Transition metal compound, catalyst for olefin polymerization, process for preparing olefin polymer by use of catalyst

ABSTRACT

A transition metal compound which is a multiple crosslinking type transition metal complex represented by the general formula (I) ##STR1## wherein M is a metallic element in the groups 3 to 10 or a lanthanoide series of the periodic table; E 1  and E 2  are each a σ-bonding or a π-bonding ligand; X is a σ-bonding ligand; L is a Lewis base; A 1 , A 2  . . . A n  and D arc each a crosslinking group; n is 2 to 4; p is 1 to 4; q is 1 to 5; r is 0 to 3; and s is 0 to 4; and catalysts for olefin polymerization containing the transition metal compound or complexes thereof and a process for preparing an olefin polymer employing the catalyst.

TECHNICAL FIELD

The present invention relates to a transition metal compound, a compoundwhich can be used as its material, a process for preparing each of thesecompounds, a catalyst for olefin polymerization using the transitionmetal compound, an olefin polymer obtained by the use of this catalyst,and a process for preparing the olefin polymer. More specifically, thepresent invention relates to a novel multiple crosslinking typetransition metal compound (multiple crosslinking metallocene complex)useful as a component of a catalyst for olefin polymerization, abisindenyl derivative usable as a ligand of this transition metalcompound, its precursor, a process for efficiently preparing each of thetransition metal compound and its precursor, a catalyst forpolymerization which has a high activity and an excellentcopolymerizability and which contains the transition metal compound andwhich is capable of forming an olefin polymer having a uniformcomposition and a narrow molecular weight distribution, an olefinhomopolymer and an olefin copolymer obtained by the use of this catalystfor polymerization, and a process for efficiently preparing each ofthese olefin polymers.

BACKGROUND ART

Heretofore, as highly active soluble catalysts for olefinpolymerization, catalysts comprising a combination of a transition metalcompound and an aluminoxane are known (Japanese Patent ApplicationLaid-open Nos. 19309/1983 and 217209/1985). Furthermore, it has beenreported that cationic species are useful as active species of thesoluble catalyst for olefin polymerization J. Am. Chem. Soc., Vol. 81,p. 81 (1959), Vol. 82, p. 1953 (1960), and Vol. 107, p. 7219 (1985)!. Inaddition, examples where each of these active species is isolated and isapplied to the olefin polymerization have been described in J. Am. Chem.Soc., Vol. 108, p. 7410 (1986), Japanese PCT Patent ApplicationLaid-open No. 502636/1989, Japanese Patent Application Laid-open No.139504/1991 and EP-A-O 468651. Other examples where this active speciesis used together with an organic aluminum compound have been describedin Japanese Patent Application Laid-open No. 207704/1991 and WO 92-1723.Moreover, an example of a catalyst for olefin polymerization whichcomprises a transition metal compound having a ligand containing an--SO₃ R group and an organic aluminum oxycompound has been described inEP-A-O No. 519746.

However, these catalysts do not always satisfy a catalytic activity forolefin polymerization, copolymerizability, and the uniformity andmolecular weight distribution of an obtained polymer.

On the other hand, a transition metal compound having abicyclopentadienyl group, i.e., a metallocene complex is particularlyhighly active and is known to be useful as a highly steric regularcatalyst. This metallocene complex can be classified into anon-crosslinking type, a single crosslinking type and a multiplecrosslinking type on the basis of the crosslinking structure of twocyclopentadienyl groups, but most of the conventional metallocenecomplexes are of the non-crosslinking type and the single crosslinkingtype.

Examples of the non-crosslinking type metallocene complex have beendisclosed or reported in U.S. Pat. No. 5200537, Japanese PatentApplication Laid-open Nos. 222177/1988, 222178/1988, 222179/1988,301704/1989 and the like, and examples of the single crosslinking typemetallocene complex have been disclosed or reported in Japanese PatentApplication Laid-open Nos. 131488/1990 and 41303/1992, "Angew. Chem.Int. Ed. Engl.", Vol. 24, Vol. 6, p. 507 (1985) and the like.

On the contrary, with regard to the multiple crosslinking type (doublecrosslinking type) metallocene complexes, their synthetic examples arelimited, and they are described only in WO 93-20113 and"Organometallics", Vol. 12, p. 1931 (1993). In addition, thesepublications have described a polymerization example of propylene in thepresence of a dimethylsilylene double crosslinking type metallocenecomplex, but the heat stability of this catalyst itself is poor. Sincethis metallocene complex has a specific crosslinking structure, theisomerization of a meso form into a racemic form occurs during thepreparation of the complex, and therefore the desired complex cannotalways be obtained.

On the other hand, "Organometallics", Vol. 12, p. 5012 (1993) hasdescribed a preparation process of a bisindenyl derivative in which thecrosslinking is made at the 2-position, but this process is notpractical, because its synthetic route is intricate.

DISCLOSURE OF THE INVENTION

The present invention has been intended under such circumstances, and anobject of the present invention is to provide (1) a novel multiplecrosslinking type transition metal compound (multiple crosslinkingmetallocene complex) useful as a component of a catalyst for olefinpolymerization, (2) a multiple crosslinking type bisindenyl derivativeusable as a ligand of this transition metal compound, (3) a process forefficiently preparing the transition metal compound of theabove-mentioned (1), (4) a bisindenyl derivative usable as a precursorof the multiple crosslinking type bisindenyl derivative of theabove-mentioned (2), (5) a process for efficiently preparing thebisindenyl derivative of the above-mentioned (4), (6) a catalyst forpolymerization which has a high activity and an excellentcopolymerizability and which is capable of forming an olefin polymerhaving a uniform composition and a narrow molecular weight distribution,(7) an olefin homopolymer or copolymer having a uniform composition anda narrow molecular weight distribution obtained by the use of thiscatalyst for polymerization, and (8) a process for efficiently preparingthe olefin homopolymer or copolymer.

Thus, the present inventors have intensively researched to achieve theabove-mentioned object, and as a result, it has been found that a novelmultiple cross-linking type transition metal compound having a specificstructure is useful as a catalytic component for olefin polymerization;a specific multiple crosslinking type bisindenyl derivative is useful asa ligand of the above-mentioned transition metal compound; and thetransition metal compound can efficiently be prepared by a specificprocess.

In addition, the present inventors have also found that a bisindenylderivative, which can be used as a precursor of the multiplecrosslinking type bisindenyl derivative useful as the ligand of theabove-mentioned transition metal compound, can efficiently be preparedby a specific process.

Furthermore, the present inventors have found that a polymerizationcatalyst, which comprises the multiple crosslinking type transitionmetal compound, an activation cocatalyst, for example, a compoundcapable of reacting with the transition metal compound or its derivativeto form an ionic complex, and if necessary, an organic aluminumcompound, has a high activity and can efficiently provide an olefinhomopolymer or copolymer having a uniform composition and a narrowmolecular weight distribution.

In consequence, the present invention has been completed on theabove-mentioned findings.

That is to say, according to the present invention, there can beprovided

(1) a transition metal compound represented by the general formula (I)##STR2## wherein M is a metallic element in the groups 3 to 10 or alanthanoide series of the periodic table; E¹ and E² are each a σ-bondingor a π-bonding ligand, and they form a cross-linking structure via(A¹)_(p), (A²)_(p), . . . (A^(n))_(p) and (D)_(s), and they may be thesame or different; X is a σ-bonding ligand, and when a plurality of Xsare present, these plural Xs may be the same or different, and each Xmay crosslink with another X, E¹, E² or Y; Y is a Lewis base, and when aplurality of Ys are present, these plural Ys may be the same ordifferent, and each Y may crosslink with another Y, E¹, E² or X; A¹, A²,. . . A^(n) are each a crosslinking group, and they may be the same ordifferent, but at least one of them comprises a crosslinked structureconsisting of carbon alone; D is a crosslinking group, and when aplurality of Ds are present, these plural Ds may be the same ordifferent; n is an integer of 2 to 4; p is an integer of 1 to 4, and therespective ps may be the same or different; q is an integer of 1 to 5(the valence of M)-2!; r is an integer of 0 to 3; and s is an integer of0 to 4, and when s is 0, (A¹)_(p), (A²)_(p), . . . (A^(n))_(p), and E²form a direct bond,

(2) a transition metal compound represented by the general formula (II)##STR3## wherein M, E¹, E², X, Y, A¹, A², . . . A^(n), n, p, q and r areas defined above,

(3) a multiple crosslinking type bisindenyl derivative represented bythe general formula (III) ##STR4## wherein I¹ and I² are each an indenylgroup or a substituted indenyl group, and they form a crosslinkingstructure via (A¹)_(p), (A²)_(p), . . . (A^(n))_(p), and they may be thesame or different; A¹, A², . . . A^(n) are each a crosslinking group,and they may be the same or different, but at least one of themcomprises a crosslinked structure consisting of carbon alone; n is 2 or3; and p is an integer of 1 to 4, and the respective ps may be the sameor different,

(4) a process for preparing a transition metal compound represented bythe general formula (II) ##STR5## wherein M, E¹, E², X, Y, A¹, A², . . .A^(n), n, p, q and r are as defined above,

said process comprising

a step of dimetallizing a compound represented by the general formula(IV) ##STR6## wherein E¹, E², A¹, A², . . . A^(n), n and p are asdefined above,

to obtain a compound represented by the general formula (V) ##STR7##wherein M¹ is an alkali metal, an alkaline earth metal-containing saltresidue or an organic aluminum residue, and E¹, E², A¹, A², . . . A^(n),n and p are as defined above,

if necessary, a step of replacing M¹ with another metal containing anorganic group or thallium, and

a step of reacting, if necessary, in the presence of a Lewis base, thecompound with a compound represented by the general formula (VI)

    MX.sub.q+2                                                 (VI)

wherein M is a metallic element in the groups 3 to 10 or a lanthanoideseries of the periodic table; X is a σ-bonding ligand; and q is aninteger of 1 to 5 (the valence of M)-2!, and when a plurality of Xs arepresent, these plural Xs may be the same or different, and each X maycrosslink with another X,

(5) a bisindenyl derivative represented by the general formula (VII)##STR8## wherein J and J' are each a group represented by the formula##STR9## (wherein R¹, R² and R³ are each a hydrogen atom, a hydrocarbongroup having 1 to 20 carbon atoms, or a silicon-containing, anoxygen-containing or a halogen-containing group, and they may be thesame or different, and when a plurality of R¹ s are present, theseplural R¹ s may be the same or different and may bond to each other toform a ring structure, and R¹ and R² or R¹ and R³ may bond to each otherto form a ring structure; and m is an integer of 1 to 4), and J and J'may be the same or different; R⁴ is a hydrogen atom, a hydrocarbon grouphaving 1 to 20 carbon atoms, or a silicon-containing, anoxygen-containing or a halogen-containing group, and a plurality of R⁴ Smay be the same or different, and they may be the same or different andmay bond to each other to form a ring structure; and k is an integer of1 to 20, but when k is 1 or 2, at least one of R⁴ s is not the hydrogenatom,

(6) a process for preparing a bisindenyl derivative represented by thegeneral formula (VII)

said process comprising

a step of reacting one or a mixture of two of compounds represented bythe general formula (VIII) ##STR10## wherein X² and X³ are each ahalogen atom, and they may be the same or different; and R¹, R², R³ andm are as defined above,

with an alkali metal or an alkaline earth metal in the presence of anorganic solvent,

a step of reacting the reaction product with a compound represented bythe general formula (IX) ##STR11## wherein y¹ and y² is each OR⁵, NR⁶ ₂,SR⁷ (wherein R⁵ to R⁷ are each a hydrogen atom, a hydrocarbon grouphaving 1 to 20 carbon atoms, or a silicon-containing, anoxygen-containing or a halogen-containing group) or a halogen atom, andthey may be the same or different; y³ and y⁴ are each O, S or NR⁸(wherein R⁸ is a hydrogen atom, a hydrocarbon group having 1 to 20carbon atoms, or a silicon-containing, an oxygen-containing or ahalogen-containing group), and they may be the same or different; and R⁴and k are as defined above,

to obtain a compound represented by the general formula (X) ##STR12##wherein G and G' are each a group represented by the general formula##STR13## (where Y⁵ is Y³ or Y⁴), and G and G' may be the same ordifferent; and R⁴ and k are as defined above, and

a step of dehydrating the obtained compound,

(7) a catalyst for olefin polymerization which comprises a transitionmetal compound represented by the above-mentioned general formula (1) or(II) and an activation cocatalyst,

(8) a catalyst for olefin polymerization which comprises (A) atransition metal compound represented by the above-mentioned generalformula (1) or (II) and (B) a compound capable of reacting with thetransition metal compound of the component (A) or its derivative to forman ionic complex,

(9) a catalyst for olefin polymerization which comprises (A) atransition metal compound represented by the above-mentioned generalformula (1) or (II), (B) a compound capable of reacting with thetransition metal compound of the component (A) or its derivative to forman ionic complex, and (C) an organic aluminum compound,

(10) an olefin polymer obtained by the use of a polymerization catalystof the above-mentioned (7) to (9), and

(11) a process for preparing an olefin polymer which comprises the stepof copolymerizing an olefin, another olefin and/or another monomer inthe presence of a catalyst for olefin polymerization of theabove-mentioned (7) to (9).

BEST MODE FOR CARRYING OUT THE INVENTION

A transition metal compound of the present invention is a novel multiplecrosslinking type compound represented by the general formula (I):##STR14##

In the above-mentioned general formula (I), M is a metallic element inthe groups 3 to 10 or a lanthanoide series of the periodic table, andtypical examples of M include titanium, zirconium, hafnium, yttrium,vanadium, chromium, manganese, nickel, cobalt, palladium and lanthanoidemetals. Above all, titanium, zirconium and hafnium are preferable fromthe viewpoint of an olefin polymerization activity. E¹ and E² are each aσ-bonding or a π-bonding ligand, and they form a crosslinking structurevia (A¹)_(p), (A²)_(p), . . . (A^(n))_(p) and (D)s and may be the sameor different. Typical examples of E¹ include a cyclopentadienyl group, asubstituted cyclopentadienyl group, an indenyl group, a substitutedindenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an amido group (--N<), a phosphide group(--P<), a hydrocarbon group (>CR-- or >C<), a silicon-containing group(>SiR-- or >Si<) (wherein R is hydrogen, a hydrocarbon group having 1 to20 carbon atoms, or a hetero-atom-containing group). Typical examples ofE² include a cyclopentadienyl group, a substituted cyclopentadienylgroup, an indenyl group, a substituted indenyl group, aheterocyclopentadienyl group, a substituted heterocyclopentadienylgroup, an amido group (--N<or -- NR--), a phosphide group (--P< or--PR--), oxygen (--O--), sulfur (--S--), selenium (--Se--), ahydrocarbon group (>C(R)₂ --, >CR-- or >C<), a silicon-containing group(>SiR--, >Si(R)₂ -- or >Si<) (wherein R is hydrogen, a hydrocarbon grouphaving 1 to 20 carbon atoms, or a hetero-atom-containing group).

Furthermore, X is a σ-bonding ligand, and when a plurality of Xs arepresent, these plural Xs may be the same or different, and each X maycrosslink with another X, E¹, E2 or Y. Typical examples of X include ahalogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxygroup having 1 to 20 carbon atoms, an aryloxy group having 6 to 20carbon atoms, an amido group having 1 to 20 carbon atoms, asilicon-containing group having 1 to 20 carbon atoms, a phosphide grouphaving 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atomsand an acyl group having 1 to 20 carbon atoms. On the other hand, Y is aLewis base, and when a plurality of Ys are present, these plural Ys maybe the same or different, and each Y may crosslink with another Y, E¹,E² or X. Typical examples of the Lewis base which is represented by Yinclude an amine, an ether, a phosphine and a thioether.

Next, A¹, A², . . . A^(n) are each a crosslinking group and they may bethe same or different, but at least one of them comprises a crosslinkedstructure consisting of carbon alone. Here, "at least one of themcomprises a crosslinked structure consisting of carbon alone" means thatat least one of them comprises a crosslinked structure represented bythe general formula ##STR15## wherein R is a hydrogen atom, a halogenatom, a hydrocarbon group having 1 to 20 carbon atoms, ahalogen-containing hydrocarbon group having 1 to 20 carbon atoms, asilicon-containing group or a hetero-atom-containing group, and pluralRs may be the same or different and may bond to each other to form aring structure; and p is an integer of 1 to 4.

Typical examples of the crosslinking group include methylene, ethylene,ethylidene, isopropylidene, cyclohexylidene, 1,2-cyclohexylene andvinylidene (CH₂ ═C═).

Other typical structures of A¹, A², . . . A^(n) include R'₂ Si, R'₂ Ge,R'₂ Sn, R'Al, R'P, R'P (═O), R'N, oxygen (--O--), sulfur (--S--) andselenium (--Se--) wherein R' is a hydrogen atom, a halogen atom, ahydrocarbon group having 1 to 20 carbon atoms, a halogen-containinghydrocarbon group having 1 to 20 carbon atoms, a silicon-containinggroup or a hetero-atom-containing group, and when two Rs are present,they may be the same or different and may bond to each other to form aring structure. Typical examples of these crosslinking groups includedimethylsilylene, tetramethyldisilylene, dimethylgermylene,dimethylstannylene, methylborilidene (CH₃ --B<), methylalumilidene (CH₃--Al<), phenylphosphilidene (Ph-P<), phenylphospholidene ##STR16##methylimide, oxygen (--O--), sulfur (--S--) and selenium (--Se--). Inaddition, examples of A¹, A², . . . A^(n) include vinylene (--CH═CH--),o-xylylene ##STR17## and 1,2-phenylene.

D represents a crosslinking group, and when a plurality of Ds arepresent, these plural Ds may be the same or different. Typical examplesof D include R"C, R"Si, R"Ge, R"Sn, B, Al, P, P(═O) and N wherein R" isa hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20carbon atoms, a halogen-containing hydrocarbon group having 1 to 20carbon atoms, a silicon-containing group or a hetero-atom-containinggroup. Furthermore, n is an integer of 2 to 4; p is an integer of 1 to4, and the respective ps may be the same or different; q is an integerof 1 to 5 (the valence of M)-2!; r is an integer of 0 to 3; and s is aninteger of 0 to 4, and when s is 0, (A¹)_(p), (A²)_(p), . . .(A^(n))_(p) and E² form a direct bond.

Of the compounds represented by the above-mentioned general formula (I),a transition metal compound represented by the following general formula(II) is preferable in which s is 0, i.e., any crosslinking group of D isnot present: ##STR18## wherein M, E¹, E², X, Y, A¹, A², . . . A^(n), n,p, q and r are as defined above.

Typical examples of such a transition metal compound include(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)zirco-niumdimethyl,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconiumdibenzyl,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)zirco-niumbis(trimethylsilyl),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconiumbis(tri-methylsilylmethyl),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconiumdimethoxide,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconiumbis(trifluoromethanesulfonate),(1,1'-dimethylsilylene)(2,2'-methylene)-bis(cyclopentadienyl)zirconiumdichloride,(1,1'-ethylene)(2,2'-methylene)-bis(cyclopentadienyl)zirconiumdichloride,(1,2'-dimethylsilylene)(2,1'-ethylene)-bis(indenyl)-zirconiumdichloride, (1,1'-dimethylsilylene)(2,2'-ethylene)-bis(indenyl)zirconiumdichloride, (1,1'-ethylene)(2,2'-dimethylsilylene)-bis(indenyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-cyclohexylidene)-bis(indenyl)zirconiumdichloride,(1,2'-dimethyl-silylene)(2,1'-isopropylidene)-bis(indenyl)zirconiumdichloride,(1,1'-isopropylidene)(2,2'-dimethylsilylene)-bis(indenyl)zirconiumdichloride,(1,1'-dimethylsilyl-ene)(2,2'-isopropylidene)-bis(indenyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(indenyl)-zirconiumdimethyl,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(indenyl)zirconiumdibenzyl,(1,1'-dimethylsilyl-ene)(2,2'-isopropylidene)-bis(indenyl)zirconiumbis(tri-methylsilyl),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(indenyl)zirconiumbis(trimethylsilylmethyl),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(indenyl)zirconiumdimethoxide,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(indenyl)zirconiumbis(trifluoromethanesulfonate),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(4,5,6,7-tetrahydroindenyl)zirconiumdichloride, (1,2'-ethylene) (2,1'-isopropylidene)-bis(indenyl)zirconiumdichloride, (1,1'-ethylene)(2,2'-isopropylidene)-bis(indenyl)-zirconiumdichloride, (1,1'-isopropylidene)(2,2'-ethylene)-bis(indenyl)zirconiumdichloride,(1,1'-isopropylidene)-(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3,4-dimethylcyclopentadienyl)(3',4'-dimethylcyclopentadienyl)-zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(4-methylcyclopentadienyl)(4'-methylcyclopentadienyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3,4,5-trimethylcyclopentadienyl)(3',4',5'-trimethylcyclopentadienyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(4-n-butylcyclopentadienyl)(4'-n-butylcyclopentadienyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)(4-tert-butylcyclopentadienyl)(4'-tert-butylcyclopentadienyl)zirco-niumdichloride,(1,2'-dimethylsilylene)(2,1'-isopropylidene)-(3-methylindenyl)(3'-methylindenyl)zirconiumdichlo-ride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3-methylindenyl)(3'-methylindenyl)zirconiumdichloride,(1,1'-isopropylidene)(2,2'-dimethylsilylene)-(3-methylindenyl)-(indenyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(4,7-dimethylindenyl)(indenyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(4,5-benzoindenyl)(indenyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(4,7-dimethylindenyl)(4',7'-dimethylindenyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(4,5-benzoindenyl)-(4,5-benzoindenyl)zirconiumdichloride,(1,1'-dimethyl-silylene)(2,2'-isopropylidene)-(3-methylindenyl)(3'-methylindenyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3-ethylindenyl)(3'-ethylindenyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3-n-butylindenyl)(3'-n-butylindenyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3-tert-butylindenyl)(3'-tert-butylindenyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3-trimethylsilylindenyl)(3'-trimethylsilylindenyl)zirconiumdichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3-benzylindenyl)(3'-benzylindenyl)zirconiumdichloride, (1,1'-dimethylsilylene)(2,2'-ethylene)-(indenyl)(cyclopenta-dienyl)zirconium dichloride,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(indenyl)(cyclopentadienyl)zirconiumdichloride,(3,3'-isopropylidene)(4,4'-isopropylidene)-(1-phosphacyclopentadienyl)(1'-phosphacyclopentadienyl)-zirconiumdichloride,(3,1'-isopropylidene)(4,2'-isopropylidene)-(1phosphacyclopentadienyl)(4'-cyclopentadienyl)zirconiumdichloride, these compounds in which zirconium is replaced withtitanium, and these compounds in which zirconium is replaced withhafnium. Needless to say, they are not restrictive. In addition, similarcompounds containing metallic elements in other groups and a lanthanoideseries of the periodic table are also usable.

The present invention is also directed to a multiple crosslinking typebisindenyl derivative represented by the general formula (III) ##STR19##wherein I¹ and I¹ are each an indenyl group or a substituted indenylgroup, and A¹, A², . . . A^(n), n and p are as defined above,

and this bisindenyl derivative can be used as a ligand in the transitionmetal compound represented by the general formula (II).

Typical examples of the multiple crosslinking type bisindenyl derivativerepresented by the general formula (III) include(1,2'-dimethylsilylene)(2,1'-ethylene)-bis(indene),(1,1'-dimethylsilylene)(2,2'-ethylene)-bis(indene),(1,1'-ethylene)(2,2'-dimethylsilylene)-bis(indene),(1,2'-dimethylsilylene)(2,1'-isopropylidene)-bis(indene),(1,1'-isopropylidene)(2,2'-dimethylsilylene)-bis(indene),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(indene),(1,2'-ethylene)(2,1'-isopropylidene)-bis(indene),(1,1'-ethylene)(2,2'-isopropylidene)-bis(indene),(1,1'-isopropylidene)(2,2'-ethylene)-bis(indene),(1,1'-dimethylsilylene)(2,2'-cyclohexylidene)-bis(indene),(1,2'-dimethylsilylene)(2,1'-isopropylidene)-(3-methylindene)(3'-methylindene),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3-methylindene)(3'-methylindene),(1,1'-isopropylidene)-(2,2'-dimethylsilylene)-(3-methylindene)(indene),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(4,7-dimethylindene)(indene),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(4,5-benzoindene)(indene),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(4,7-dimethylindene)(4',7'-dimethylindene),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(4,5-benzoindene)(4,5-benzoindene),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3-methylindene)(3'-methylindene),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3-methylindene)(3'-ethylindene),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3-n-butylindene)(3'-n-butylindene),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3-tert-butylindene)(3'-tert-butylindene),(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3-trimethylsilylindene)(3'-trimethylsilylindene),(1,1'-dimethylsilylene)(2,2'-isopropylidnene)-(3-benzylindene)(3'-benzylindene),(1,1'-dimethylsilylene)(2,2'-ethylene)-(indene)(cyclopentadiene) and(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(indene)(cyclopentadiene).

Furthermore, the transition metal compound represented by the generalformula (II) of the present invention can be prepared by any of variousmethods, but according to a process of the present invention, it caneasily be prepared as follows.

In the first place, a compound represented by the general formula (IV)##STR20## wherein E¹, E², A¹, A², . . . A^(n), n and p are as definedabove,

is dimetallized with a compound represented by the general formula (XI)

    R.sup.8 M.sup.1                                            (XI)

wherein R⁸ is a conjugated base in which an acid dissociation constant(pKa value) is 25 or more in terms of R⁸ -H; and M¹ is an alkali metal,an alkaline earth metal-containing salt residue or an organic aluminumresidue, in a suitable solvent, for example, an ether such as diethylether, diisopropyl ether, di-n-butyl ether, 1,2-diethoxyethane,1,2-dimethoxyethane or tetrahydrofuran, or a hydrocarbon such asn-hexane, n-pentane, n-octane, benzene, toluene or xylene to obtain acompound represented by the general formula (V) ##STR21## wherein M¹,E¹, E², A¹, A², . . . A^(n), n and p are as defined above.

In the above-mentioned general formula (XI), as R⁸, a conjugated base inwhich an acid dissociation constant (pKa value) is 30 or more in termsof R⁸ -H is particularly preferable from the viewpoint of a productionefficiency, and typical examples of R⁸ include amides such asdiisopropylamide, diethylamide, dimethylamide, piperidide andpyrrolidide, and hydrocarbon anions having 1 to 20 carbon atoms such asa phenyl anion, a methyl anion, an n-butyl anion, a cyclohexyl anion, abenzyl anion, a vinyl anion and an allyl anion.

Furthermore, M¹ is an alkali metal, an alkaline earth metal-containingsalt residue or an organic aluminum residue, and examples of the alkalimetal include lithium, sodium and potassium. An example of the alkalineearth metal-containing salt residue is a compound represented by MgX¹(X¹ is a halogen atom such as bromine, iodine or chlorine), and anexample of the organic aluminum residue is a compound represented byAlR"'₂ (R"' is a hydrocarbon group having 1 to 20 carbon atoms, and twoR"'s may be the same or different). The concentration of a compoundrepresented by the above-mentioned general formula (IV) isadvantageously in the range of 0.01 to 5 mol/liter, preferably 0.1 to 3mol/liter. No particular restriction is put on a reaction temperature ofthis dimetallization, and the reaction temperature is selected in therange of from a solidifying point of the solvent to a boiling point ofthe solvent, but it is preferably within the range of -100° to 100° C.,more preferably -80° to 30° C. In addition, the reaction temperaturedoes not always have to be maintained at a constant temperature. Noparticular restriction is put on a mixing order of the materialcompounds, and the compound represented by the general formula (XI) maybe added to the compound represented by the general formula (IV) andvice versa, but the former is preferable. With regard to a use ratiobetween the compound represented by the general formula (IV) and thecompound represented by the general formula (XI), it is preferred to usethe compound represented by the general formula (XI) in a ratio of 1 to4 mol, preferably 1.8 to 2.2 mol with respect to 1 mol of the compoundrepresented by the general formula (IV).

Next, the thus obtained compound represented by the general formula (V)is then reacted with a compound represented by the general formula (VI)

    Mx.sub.q+2                                                 (VI)

wherein M, X and q are as defined above),

in a suitable solvent such as the above-mentioned solvent and, ifnecessary, in the presence of a Lewis base, thereby obtaining atransition metal compound represented by the general formula (II).

Examples of the compound represented by the above-mentioned generalformula (VI) include TiCl₄, TiBr₄, ZrCl₄, HfCl₄, YCl₃, ScCl₃, M'Cl₃ (M'is a lanthanoide metal), VCl₃, NbCl₅, TaCl₅, CrCl₃, MoCl₅, WCl₆, FeCl₂,RuCl₂, NiCl₂ and PdCl₂.

With regard to a use ratio between the compound represented by thegeneral formula (V) and the compound represented by the general formula(VI), it is preferred to use the compound represented by the generalformula (VI) in a ratio of 0.1 to 10 mol, preferably 0.5 to 2 mol withrespect to 1 mol of the compound represented by the general formula (V).No particular restriction is put on a mixing order of both thecompounds. In addition, the solvent, concentration and temperature inthis reaction are the same as in the case of the dimetallizing reactionof the compound represented by the general formula (IV).

According to an alternative method, 1 mol of the compound represented bythe general formula (V) is reacted with about 1 to 4 mol, preferablyabout 1.8 to 2.2 mol of tin trialkylhalide, silicon trialkylhalide orgermanium trialkylhalide to replace M¹ with another metal containing anorganic group such as trialkyltin, trialkylsilicon or trialkylgermanium,or the compound represented by the general formula (V) is reacted withabout 1 to 4 mol, preferably about 1.8 to 2.2 mol of an alkoxythalliumto replace M¹ with thallium (first reaction); and this compound, inwhich M¹ is replaced with the other metal containing the organic groupor thallium, is then reacted with the compound represented by thegeneral formula (VI) in a ratio of about 1 to 4 mol, preferably about1.8 to 2.2 mol of the latter to 1 mol of the former, if necessary, inthe presence of a Lewis base (second reaction), thereby obtaining thetransition metal compound represented by the general formula (II). Inthis reaction, no particular restriction is put on a mixing order of thecompounds in both the first reaction and the second reaction. Inaddition, the solvent, concentration and temperature in the firstreaction are the same as in the case of the dimetallizing reaction ofthe compound represented by the general formula (IV). In the secondreaction, halogenated hydrocarbons such as dichloromethane andchloroform as well as a nitrile such as acetonitrile can be used as thesolvent in addition to the above-mentioned solvents. The concentrationand temperature in the second reaction are the same as in the case ofthe dimetallizing reaction of the compound represented by the generalformula (IV).

Furthermore, the present invention is also directed to a bisindenylderivative represented by the following general formula (VII) which isuseful as a precursor of a multiple crosslinking type bisindenylderivative represented by the above-mentioned general formula (III)usable as a ligand in the transition metal compound, and a process forpreparing the bisindenyl derivative: ##STR22## wherein J and J' are eacha group represented by the formula ##STR23## (wherein R¹, R² and R³ areeach a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,or a silicon-containing, an oxygen-containing or a halogen-containinggroup, and they may be the same or different, and when a plurality of R¹s are present, these plural R¹ s may be the same or different and maybond to each other to form a ring structure, and R¹ and R² or R¹ and R³may bond to each other to form a ring structure; and m is an integer of1 to 4), and J and J' may be the same or different; R⁴ is a hydrogenatom, a hydrocarbon group having 1 to 20 carbon atoms, or asilicon-containing, an oxygen-containing or a halogen-containing group,and a plurality of R⁴ s may be the same or different, and they may bethe same or different and may bond to each other to form a ringstructure; and k is an integer of 1 to 20, but when k is 1 or 2, atleast one of R⁴ s is not the hydrogen atom.

Next, the process for preparing the bisindenyl derivative represented bythe general formula (VII) will be described. A mixture comprising one ortwo of compounds represented by the general formula (VIII) ##STR24##wherein X² and X³ are each a halogen atom, and they may be the same ordifferent; and R¹, R², R³ and m are as defined above,

is reacted with an alkali metal or an alkaline earth metal at atemperature in the range of -50° to 100° C., preferably 0° to 70° C.(however, when the boiling point of the solvent is lower than thistemperature, this boiling point is regarded as an upper limit) in asuitable organic solvent, for example, an ether such as diethyl ether,diisopropyl ether, di-n-butyl ether, 1,2-diethoxyethane,1,2-dimethoxyethane or tetrahydrofuran, or a hydrocarbon such asn-pentane, n-octane, n-hexane, toluene or xylene, thereby obtaining acompound represented by the general formula (XII) ##STR25## wherein M²is an alkali metal or an alkaline earth metal; e is 0 in the case thatM² is the alkali metal or 1 in the case that M² is the alkaline earthmetal; and R¹, R², R³, X² and X³ and m are as defined above.

In this case, a preferable example of the alkali metal is lithium,potassium or sodium, and an preferable example of the alkaline earthmetal is magnesium. A molar ratio of the compound represented by thegeneral formula (XIII) to the above-mentioned metal is in the range of0.25 to 16, preferably 0.5 to 8. Moreover, no particular restriction isput on a mixing order of these materials.

Furthermore, the concentration of the compound represented by thegeneral formula (XII) is preferably in the range of 0.01 to 5 mol/liter,preferably 0.1 to 3 mol/liter. If this concentration is less than 0.01mol/liter, a volume efficiency is low and productivity is also low, andif it is more than 5 mol/liter, the production efficiency of thecompound represented by the general formula (XII) deteriorates.

Next, a compound represented by the general formula (IX) ##STR26##wherein Y¹ and Y² is each OR⁵, NR⁶ ₂, SR⁷ (wherein R⁵ to R⁷ are each ahydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or asilicon-containing, an oxygen-containing or a halogen-containing group)or a halogen atom, and they may be the same or different; Y³ and Y⁴ areeach O, S or NR⁸ (wherein R⁸ is a hydrogen atom, a hydrocarbon grouphaving 1 to 20 carbon atoms, or a silicon-containing, anoxygen-containing or a halogen-containing group), and they may be thesame or different; and R⁴ and k are as defined above,

is added to the reaction solution containing the compound represented bythe general formula (XII) without isolating the compound therefrom, andthe compound of the general formula (IX) is reacted with the compound ofthe general formula (XII) at a temperature of -100° to 100° C.,preferably -80° to 50° C., thereby obtaining a compound represented bythe general formula (X) ##STR27## wherein G and G' are each a grouprepresented by the general formula ##STR28## and G and G' may be thesame or different; and R⁴ and k are as defined above.

In this reaction, no particular restriction is put on the concentrationof the compound represented by the general formula (X) in the reactionsolution. A molar ratio of the compound represented by the generalformula (XII) to the compound represented by the general formula (IX) issuitably within the range of 1 to 10, preferably 2 to 4. Moreover, noparticular restriction is put on a mixing order of these compounds.

Furthermore, the thus obtained compound represented by the generalformula (X) is dehydrated in a suitable solvent to obtain the bisindenylderivative represented by the general formula (VII).

No particular restriction is put on the solvent for use in thisdehydrating reaction, and any solvent can be used, so far as it candissolve the compound represented by the general formula (X) and it isinert to the reaction. In addition, in this dehydrating reaction, aBrφnsted acid or a Lewis acid is usually used. Here, as the Brφnstedacid, there can preferably be used an acid having an acid dissociationconstant (pKa value) of -6 or less, and examples of such an acid includehydrochloric acid, sulfuric acid, perchloric acid and p-toluenesulfonicacid. On the other hand, examples of the Lewis acid include I₂, AlCl₃,AlBr₃, MgCl₂, ZnCl₂, ZnI₂, ZnBr₂, SnCl₄, TiCl₄, ZrCl₁, HfCl₄, YCl₃,FeCl₃ and CuCl₂. No particular restriction is put on the amount of theBrφnsted acid or the Lewis acid to be used, and the amount may be acatalytic amount.

The temperature of the dehydrating reaction is usually selected in therange of -100° to 300° C., preferably 0° to 100° C.

Of the bisindenyl derivatives represented by the above-mentioned generalformula (VII), the bisindenyl derivatives in which k is 1 arepreferable.

Typical examples of the bisindenyl derivatives represented by theabove-mentioned general formula (VII) include(2,2'-isopropylidene)-bis(indene),(2,2'-isopropylidene)-(3-methylindene)(3'-methylindene),(2,2'-isopropylidene)-(3-methylindene)(indene),(2,2'-isopropylidene)(4,7-dimethylindene)(indene),(2,2'-isopropylidene)-(4,5-benzoindene)(indene),(2,2'-isopropylidene)-(4,7-dimethylindene), (4',7'-dimethylindene),(2,2'-isopropylidene)-(4,5-benzoindene)(4,5-benzoindene),(2,2'-isopropylidene)-(3-methylindene)(3'-methylindene),(2,2'-isopropylidene)-(3-ethylindene)(3'-methylindene),(2,2'-isopropylidene)-(3-n-butylindene)(3'-n-butylindene),(2,2'-isopropylidene)-(3-tert-butylindene)(3'-tert-butylindene),(2,2'-isopropylidene)-(3-trimethysilylindene)(3'-trimethylsilylindene),(2,2'-isopropylidene)-(3-benzylindene)(3'-benzylindene) and(2,2'-cyclohexylidene)-bis(indene).

The catalyst for olefin polymerization of the present invention is acatalyst comprising (A) the transition metal compound represented by thegeneral formula (I) or (II), an activation cocatalyst, for example, (B)a compound capable of reacting with the transition metal compound of thecomponent (A) or its derivative to form an ionic complex, and ifnecessary, (C) an organic aluminum compound.

In this catalyst for polymerization, the transition metal compoundsrepresented by the general formula (I) and (II), which can be used asthe component (A), may be used singly or in a combination of two or morethereof.

In this catalyst for polymerization of the present invention, thecomponent (A) and the activation cocatalyst are used. No particularrestriction is put on the activation cocatalyst, but for example, as thecomponent (B), there can be used a compound capable of reacting with thetransition metal compound of the component (A) or its derivative to forman ionic complex.

As examples of this component (B), an ionic compound (B-1) capable ofreacting with the transition metal compound of the component (A) to forman ionic complex, an aluminoxane (B-2) or a Lewis acid (B-3) arepreferable, because they have a high polymerization activity and canreduce a catalyst cost.

As the component (B-1), any compound can be used, so far as it can reactwith the transition metal compound of the component (A) to form an ioniccomplex, but compounds represented by the following general formulae(XIII) and (XIV) can be suitably used from the viewpoints of theparticularly efficient formation of activation points for thepolymerization and the like:

    ( L.sup.1 -R.sup.9 !.sup.h+).sub.a ( Z!.sup.-).sub.b       (XIII)

    ( L.sup.2 !.sup.h+).sub.a ( Z!.sup.-).sub.b                (XIV)

wherein L² is M⁴, R¹⁰ R¹¹ M⁵, R¹² ₃ C or R¹³ M⁵ ; L¹ is a Lewis base;Z!⁻ is a non-coordinating anion Z¹ !⁻ or Z² !⁻ ; here Z¹ !⁻ is an anionin which a plurality of groups are bonded to an element, i.e., M³ G¹ G². . . G^(f) ! wherein M³ is an element in the groups 5 to 15, preferablythe groups 13 to 15 of the periodic table; G¹ to G^(f) are each ahydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbonatoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy grouphaving 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,an aryloxy group having 6 to 20 carbon atoms, an alkylaryl group having7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, ahalogen-substituted hydrocarbon group having 1 to 20 carbon atoms, anacyloxy group having 1 to 20 carbon atoms, an organic metalloid group ora hetero-atom-containing hydrocarbon group having 2 to 20 carbon atoms,and two or more of G¹ to G^(f) may form a ring; f is an integer of (avalence of the central metal M³)+1!; Z² !⁻ is a Brφnsted acid single inwhich a logarithm (pKa) of a reciprocal number of an acid dissociationconstant is -10 or less, a conjugated base of a combination of theBrφnsted acid and a Lewis acid, or a conjugated base usually defined asa superstrong acid, and Z² !⁻ may be coordinated with a Lewis base; R⁹is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an arylgroup, an alkylaryl group or an arylalkyl group having 6 to 20 carbonatoms; R¹⁰ and R¹¹ are each a cyclopentadienyl group, a substitutedcyclopentadienyl group, an indenyl group or a fluorenyl group; R¹² is analkyl group, an aryl group, an alkylaryl group or an arylalkyl grouphaving 1 to 20 carbon atoms; R¹³ is a large cyclic ligand such astetraphenylporphyrin or phthalocyanine; h is an ionic valence of L¹ -R⁹! or L² ! and it is an integer of 1 to 3; a is an integer of 1 or more;b is (h×a); M⁴ is an element in the groups 1 to 3, 11 to 13 and 17 ofthe periodic table; and M⁵ is an element in the groups 7 to 12 of theperiodic table.

Here, typical examples of L¹ include amines such as ammonia,methylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, N,N-dimethylaniline, trimethylamine, triethylamine,tri-n-butylamine, methyldiphenylamine, pyridine,p-bromo-N,N-dimethylaniline and p-nitro-N,N-dimethylaniline, phosphinessuch as triethylphosphine, triphenylphosphine and diphenylphosphine, athioether such as tetrahydrothiophene, an ester such as ethyl benzoate,and nitriles such as acetonitrile and benzonitrile.

Typical examples of R⁹ include hydrogen, a methyl group, an ethyl group,a benzyl group and a trityl group, and typical examples of R¹⁰ and R¹¹include a cyclopentadienyl group, a methylcyclopentadienyl group, anethylcyclopentadienyl group and a pentamethylcyclopentadienyl group.Typical examples of R¹² include a phenyl group, a p-tolyl group and ap-methoxyphenyl group, and typical examples of R¹³ includetetraphenylporphine, phthalocyanine, allyl and methallyl. Typicalexamples of M⁴ include Li, Na, K, Ag, Cu, Br, I and I₃, and typicalexamples of M⁵ include Mn, Fe, Co, Ni or Zn.

Furthermore, typical examples of M³ in Z¹ !⁻, i.e., M³ G¹ G² . . . G^(f)! include B, Al, Si, P, As and Sb, and above all, B and Al arepreferable. Typical examples of G¹, G² to G^(f) include dialkylaminogroups such as a dimethylamino group and a diethylamino group, alkoxygroups and aryloxy groups such as a methoxy group, an ethoxy group, ann-butoxy group and a phenoxy group, hydrocarbon groups such as a methylgroup, an ethyl group, an n-propyl group, an isopropyl group, an n-butylgroup, an isobutyl group, an n-octyl group, an n-eicosyl group, a phenylgroup, a p-tolyl group, a benzyl group, a 4-t-butylphenyl group and a3,5-dimethylphenyl group, halogen atoms such as fluorine, chlorine,bromine and iodine, hetero-atom-containing hydrocarbon groups such as ap-fluorophenyl group, a 3,5-difluorophenyl group, a pentachlorophenylgroup, a 3,4,5-trifluorophenyl group, a pentafluorophenyl group, a3,5-bis(trifluoromethyl)phenyl group and a bis(trimethylsilyl)methylgroup, and organic metalloid groups such as a pentamethylantimony group,a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group,a dicyclohexylantimony group and a diphenylboron group.

Typical examples of the non-coordinating anion, i.e., the conjugatedbase Z² !⁻ which is the Brφnsted acid single having a pKa of -10 or lessor the combination of the Brφnsted acid and the Lewis acid includetrifluoromethanesulfonic acid anion (CF₃ SO₃)⁻,bis(trifluoromethane-sulfonyl)methyl anion,bis(trifluoromethanesulfonyl)benzyl anion,bis(trifluoromethanesulfonyl)amide, perchloric acid anion (ClO₄)⁻,trifluoroacetic acid anion (CF₃ CO₂)⁻, hexafluoroanitimony anion(SbF₆)⁻, fluorosulfonic acid anion (FSO₃)⁻, chlorosulfonic acid anion(ClSO₃)⁻, fluorosulfonic acid anion-5-antimony fluoride (FSO₃ -SbF₅)⁻,fluorosulfonic acid anion-5-arsenic fluoride (FSO₃ -AsF₅)⁻ andtrifluoromethanesulfonic acid-5-antimony fluoride (CF₃ SO₃ -SbF₅)⁻.

Typical examples of the ionic compound, i.e., the (B-1) componentcompound capable of reacting with the transition metal compound of theabove-mentioned component (A) to form an ionic complex includetriethylammonium tetraphenylborate, tri-n-butylammoniumtetraphenylborate, trimethylammonium tetraphenylborate,tetraethylammonium tetraphenylborate, methyl(tri-n-butyl)ammoniumtetraphenylborate, benzyl(tri-n-butyl)ammonium tetraphenylborate,dimethyldiphenylammonium tetraphenylborate, triphenyl(methyl)ammoniumtetraphenylborate, trimethylanilinium tetraphenylborate,methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate,methyl(2-cyanopyridinium) tetraphenylborate, triethylammoniumtetrakis(pentafluorophenyl)borate, tri-n-butylammoniumtetrakis(pentafluorophenyl)borate, triphenylammoniumtetrakis(pentafluorophenyl)borate, tetra-n-butylammoniumtetrakis(pentafluorophenyl)borate, tetraethylammoniumtetrakis(pentafluorophenyl)borate, benzyl(tri-n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, methyldiphenylammoniumtetrakis(pentafluorophenyl)borate, triphenyl(methyl)ammoniumtetrakis(pentafluorophenyl)borate, methylaniliniumtetrakis(pentafluorophenyl)borate, dimethylaniliniumtetrakis(pentafluorophenyl)borate, trimethylaniliniumtetrakis(pentafluorophenyl)borate, methylpyridiniumtetrakis(pentafluorophenyl)borate , benzylpyridiniumtetrakis(pentafluorophnlurophenyl)borate, methyl(2-cyanopyridinium)tetrakis(pentafluorophenylu)borate, benzyl(2-cyanopyridinium)tetrakis(pentafluorophenyl)borate, methyl(4-cyanopyridinium)tetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, dimethylanilinium tetrakisbis(3,5-ditrifluoromethyl)phenyl!borate, ferrocenium tetraphenylborate,silver tetraphenylborate, trityl tetraphenylborate,tetraphenylporphyrinmanganese tetraphenylborate, ferroceniumtetrakis(pentafluorophenyl)borate, (1,1'-dimethylferrocenium)tetrakis(pentafluorophenyl)borate, decamethylferroceniumtetrakis(pentafluorophenyl)borate, silvertetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, sodiumtetrakis(pentafluorophenyl)borate, tetraphenylporphyrinmanganesetetrakis(pentafluorophenyl)borate, silver tetrafluoroborate, silverhexafluorophosphate, silver hexafluoroarsenate, silver perchlorate,silver trifluoroacetate and silver trifluoromethanesulfonate.

The ionic compounds, which can be used as the component (B-1), capableof reacting with the transition metal compound of the component (A) toform an ionic complex may be used singly or in a combination of two ormore thereof.

On the other hand, examples of the aluminoxane which is the component(B-2) include a chain aluminoxane represented by the general formula(XV) ##STR29## wherein R¹⁴ is a hydrocarbon group such as an alkylgroup, an alkenyl group, an aryl group or an arylalkyl group having 1 to20 carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom, anda plurality of R¹⁴ S may be the same or different; and w is an averagepolymerization degree and it is usually an integer of 2 to 50,preferably 2 to 40,

and a cyclic aluminoxane represented by the general formula (XVI)##STR30## wherein R¹⁴ and w are the same as in the above-mentionedgeneral formula (XV).

A method for preparing the above-mentioned aluminoxane comprises thestep of bringing an alkylaluminum into contact with a condensing agentsuch as water, but its means is not particularly limited and a knownprocedure can be used to carry out a reaction. For example, there are(1) a method which comprises dissolving an organic aluminum compound inan organic solvent, and then bringing the solution into contact withwater, (2) a method which comprises first adding an organic aluminumcompound to a polymerization system at the time of polymerization, andthen adding water, (3) a method which comprises reacting an organicaluminum compound with crystal water contained in a metallic salt orwater adsorbed on an inorganic material or an organic material, and (4)a method which comprises reacting a tetraalkyldialuminoxane withtrialkylaluminum, and then reacting the resultant reaction product withwater. In this connection, the aluminoxane which is insoluble in tolueneis also usable.

These aluminoxanes may be used singly or in a combination of two or morethereof.

No particular restriction is put on the Lewis acid which is thecomponent (B-3), and it may be an organic compound or a solid inorganiccompound. As the organic compound, a boron compound or an aluminumcompound can preferably be used, and as the inorganic compound, amagnesium compound or an aluminum compound can preferably be used,because they can efficiently form activation points. Examples of thealuminum compound as the organic compound includebis(2,6-di-t-butyl-4-methylphenoxy)aluminummethyl and(1,1-bi-2-naphthoxy)aluminummethyl, and examples of the magnesiumcompound include magnesium chloride and diethoxymagnesium. Examples ofthe aluminum compound as the inorganic compound include aluminum oxideand aluminum chloride, and examples of the boron compound includetriphenylboron, tris(pentafluorophenyl)boron, tris3,5-bis-(trifluoromethyl)phenyl!boron, tris(4-fluoromethyl)-phenyl!boron, trimethylboron, triethylboron,tri-n-butylboron, tris(fluoromethyl)boron, tris(pentafluoroethyl)boron,tris(nonafluorobutyl)boron, tris(2,4,6-trifluorophenyl)boron,tris(3,5-difluoro)boron, tris 3,5-bis(trifluoromethyl)phenyl!boron,bis(pentafluorophenyl)fluoroboron, diphenylfluoroboron,bis(pentafluorophenyl)chloroboron, dimethylfluoroboron,diethylfluoroboron, di-n-butyl-fluoroboron,pentafluorophenyldifluoroboron, phenyldifluoroboron,pentafluorophenyldichloroboron, methyldifloroboron, ethyldifluoroboronand n-butyldifluoroboron.

These Lewis acids may be used singly or in a combination of two or morethereof.

A molar ratio of the catalytic component (A) to the catalytic component(B) in the catalyst for polymerization of the present invention ispreferably in the range of 10:1 to 1:100, more preferably 2:1 to 1:10 inthe case that the compound (B-1) is used as the catalytic component (B),and if the molar ratio deviates from the above-mentioned range, thecatalyst cost per unit weight of an obtained polymer increases, which isnot practical. In the case that the compound (B-2) is used, the molarratio is preferably in the range of 1:1 to 1:1000000, more preferably1:10 to 1:10000. If the molar ratio deviates from the above-mentionedrange, the catalyst cost per unit weight of an obtained polymerincreases, which is not practical.

A molar ratio of the catalytic component (A) to the catalytic component(B-3) is preferably in the range of 10:1 to 1:2000, more preferably 5:1to 1:1000, most preferably 2:1 to 1:500, and if the molar ratio deviatesfrom the above-mentioned range, the catalyst cost per unit weight of anobtained polymer increases, which is not practical. Furthermore, as thecatalytic component (B), the compounds (B-1), (B-2) and (B-3) may beused singly or in a combination of two or more thereof.

The catalyst for polymerization of the present invention may contain theabove-mentioned components (A) and (B) as the main components, oralternatively, it may contain the components (A) and (B) as well as anorganic aluminum compound (C) as the main components.

Here, as the organic aluminum compound of the component (C), there canbe used a compound represented by the general formula (XVII)

    R.sup.15.sub.v AlQ.sub.3-v                                 (XVII)

wherein R¹⁵ is an alkyl group having 1 to 10 carbon atoms; Q is ahydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an arylgroup having 6 to 20 carbon atoms or a halogen atom; and v is an integerof 1 to 3.

Typical examples of the compound represented by the general formula(XVII) include trimethylaluminum, triethylaluminum,triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride,diethylaluminum chloride, methylaluminum dichloride, ethylaluminumdichloride, dimethylaluminum fluoride, diisoblutylaluminum hydride,diethylaluminum hydride and ethylaluminum sesquichloride.

These organic aluminum compounds may be used singly or in a combinationof two or more thereof.

A molar ratio of the catalytic component (A) to the catalytic component(C) is preferably in the range of 1:1 to 1:10000, more preferably 1:5 to1:2000, most preferably 1:10 to 1:1000. The employment of the catalyticcomponent (C) enables a polymerization activity per transition metal toimprove, but if the amount of the catalytic component (C) is excessivelylarge, particularly if it is in excess of the above-mentioned range, theorganic aluminum compound is used in vain and it remains in largequantities in the polymer. Conversely, if it the amount of the catalyticcomponent (C) is small, a sufficient catalytic activity cannot beobtained unpreferably sometimes.

In the present invention, at least one of the catalytic components, whenused, may be supported on a suitable carrier. No particular restrictionis put on the kind of carrier, and any of an inorganic oxide carrier,another inorganic carrier and an organic carrier can be used, but theinorganic oxide carrier or the other inorganic carrier is particularlypreferable from the viewpoint of morphology control.

Typical examples of the inorganic oxide carrier include SiO₂, Al₂ O₃,MgO, ZrO₂, TiO₂, Fe₂ O₃, B₂ O₃, CaO, ZnO, BaO, ThO₂ and mixtures thereofsuch as silica-alumina, zeolites, ferrites and glass fibers. Above all,SiO₂ and Al₂ O₃ are particularly preferable. The above-mentionedinorganic oxide carrier may contain a small amount of a carbonate, anitrate, a sulfate or the like.

On the other hand, examples of usable carriers other than mentionedabove include magnesium compounds represented by the general formulaMgR¹⁶ _(x) X⁴ _(y) typified by magnesium compounds such as MgCl₂ andMg(OC₂ H₅)₂, and complexes thereof. In this general formula, R¹⁶ is analkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20carbon atoms or an aryl group having 6 to 20 carbon atoms; X⁴ is ahalogen atom or an alkyl group having 1 to 20 carbon atoms; x is 0 to 2;and y is 0 to 2, and x+y═2. A plurality of R¹⁶ s and X⁴ S may be thesame or different.

Examples of the organic carrier include polymers such as polystyrenes,styrene-divinylbenzene copolymers, polyethylenes, polypropylenes,substituted polystyrenes and polyacrylates, starch and carbon.

Preferable examples of the carrier which can be used in the presentinvention include MgCl₂, MgCl(OC₂ H₅), Mg(OC₂ H₅)₂, SiO₂ and Al₂ O₃. Thecharacteristics of the carrier depend upon its kind and preparationmethod, but the average particle diameter of the carrier is usually inthe range of 1 to 300 μm, preferably 10 to 200 μm, more preferably 20 to100 μm.

If the particle diameter is small, the amount of a fine powder in thepolymer increases, and if it is large, the amount of the coarseparticles increase in the polymer, which leads to the deterioration ofbulk density and the clogging of a hopper.

The specific surface area of the carrier is usually in the range of 1 to1000 m² /g, preferably 50 to 500 m² /g, and the pore volume of thecarrier is usually in the range of 0.1 to 5 cm³ /g, preferably 0.3 to 3cm³ /g.

If either of the specific surface area or the pore volume deviates fromthe above-mentioned range, the catalytic activity deteriorates onoccasion. The specific surface area or the pore volume can be determinedon the basis of the volume of a nitrogen gas adsorbed, for example, by aBET method J. Am. Chem. Soc., Vol. 60, p. 309 (1983)!.

Furthermore, the carrier is suitably calcined usually at 150° to 1000°C., preferably 200° to 800° C. prior to its use.

In the case that at least one of the catalytic components is supportedon the above-mentioned carrier, at least one of the catalytic components(A) and (B), preferably both of the catalytic components (A) and (B) aresupported, which is desirable from the viewpoints of morphology controland applicability to a process such as gaseous phase polymerization.

No particular restriction is put on a method for supporting at least oneof the catalytic components (A) and (B) on the carrier, but there can beused, for example, (1) a method which comprises mixing at least one ofthe catalytic components (A) and (B) with the carrier, (2) a methodwhich comprises first treating the carrier with an organic aluminumcompound or a halogen-containing silicon compound, and then mixing atleast one of the catalytic components (A) and (B) with the treatedcarrier in an inert solvent, (3) a method which comprises reacting thecarrier, one or both of the catalytic components (A) and (B) and anorganic aluminum compound or a halogen-containing silicon compound, (4)a method which comprises supporting the component (A) or the component(B) on the carrier, and then mixing the carrier with the component (B)or the component (A), (5) a method which comprises mixing the carrierwith a catalytic reaction product of the component (A) and the component(B), or (6) a method which comprises carrying out a catalytic reactionof the component (A) and the component (B) in the presence of thecarrier.

In the reaction of the above-mentioned methods (4), (5) and (6), theorganic aluminum compound which is the component (C) can be added.

The thus obtained catalyst may be used for the polymerization after ithas been taken out as a solid by distilling off a solvent, or it may beused as it is without isolation.

In the present invention, the catalyst can be prepared by carrying outan operation of supporting at least one of the component (A) and thecomponent (B) on the carrier in a polymerization system. For example, amethod can be employed which comprises adding at least one of thecomponents (A) and (B), the carrier and if necessary, the organicaluminum compound as the above-mentioned component (C) to the system,further adding an olefin such as ethylene as much as a pressure of fromatmospheric pressure to 20 kg/cm², and then carrying outprepolymerization at -20° to 200° C. for a period of 1 minute to 2 hoursto form catalyst particles.

In the present invention, a weight ratio of the compound component (B-1)to the carrier is preferably in the range of 1:5 to 1:10000, morepreferably 1:10 to 1:500; a weight ratio of the compound component (B-2)to the carrier is preferably in the range of 1:0.5 to 1:1000, morepreferably 1:1 to 1:50; and a weight ratio of the compound component(B-3) to the carrier is preferably in the range of 1:5 to 1:10000, morepreferably 1:10 to 1:500. In the case that two or more kinds ofcatalytic components (B) is used in the form of a mixture, the weightratios of these components (B) to the carrier are desirably within theabove-mentioned ranges, respectively. A weight ratio of the component(A) to the carrier is preferably 1:5 to 1:10000, more preferably 1:10 to1:500.

If the use ratio of the component (B) the component (B-1), the component(B-2) or the component (B-3)! to the carrier, or the use ratio of thecomponent (A) to the carrier deviates from the above-mentioned range,the activity deteriorates on occasion. The average particle diameter ofthe thus prepared catalyst for polymerization according to the presentinvention is usually in the range of 2 to 200 μm, preferably 10 to 150μm, more preferably 20 to 100 μm, and the specific surface area of thecatalyst is usually in the range of 20 to 1000 m² /g, preferably 50 to500 m² /g. If the average particle diameter of the catalyst is less than2 μm, the amount of a fine powder in the polymer increases sometimes,and if it is more than 200 μm, the amount of the coarse particlesincrease in the polymer sometimes. If the specific surface area of thecatalyst is less than 20 m² /g, the activity deteriorates on occasion,and it is more than 1000 m² /g, the bulk density of the polymerdeteriorates sometimes. Furthermore, in the catalyst of the presentinvention, the amount of the transition metal in 100 g of the carrier isusually in the range of 0.05 to 10 g, preferably 0.1 to 2 g. If theamount of the transition metal deviates from the above-mentioned range,the activity deteriorates on occasion.

This technique of supporting the components on the carrier enables theformation of the industrially advantageous polymer having the high bulkdensity and an excellent particle diameter distribution.

According to the preparation method of the olefin polymer regarding thepresent invention, the homopolymerization of an olefin or thecopolymerization of an olefin and another olefin and/or another monomer(i.e., the copolymerization of different kinds of olefins, thecopolymerization of an olefin and another monomer, or the copolymer ofdifferent kinds of olefins and another monomer) can be suitably carriedout by the use of the above-mentioned catalyst for polymerization.

No particular restriction is put on the kind of olefins, but α-olefinshaving 2 to 20 carbon atoms are preferable. Examples of the α-olefinsinclude ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene,1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, styrene,p-methylstyrene, isopropylstyrene and t-butylstyrene. Theabove-mentioned other olefin can also suitably be selected from theseolefins mentioned above.

In the present invention, the above-mentioned olefins may be used singlyor in a combination of two or more thereof. In the case that two or moreolefins are copolymerized, these olefins can optionally be combined. Atthis time, for example, when propylene is copolymerized with ethylene orethylene is copolymerized with an α-olefin having 3 to 10 carbon atoms,a copolymerization ratio (molar ratio) of propylene and ethylene, orethylene and the α-olefin having 3 to 10 carbon atoms is usuallyselected in the range of 99.9:0.1 to 0.1 to 99.9, preferably 99.5:0.5 to75.0:25.0.

In the present invention, the above-mentioned olefin may becopolymerized with another monomer, and examples of the other monomerwhich can be used at this time include chain diolefins such asbutadiene, isoprene and 1,5-hexadiene, cyclic olefins such asnorbornene, 1,4,5,8-dimethanol-1,2,3,4,4a,5,8,8a-octahydronaphthaleneand 2-norbornene, cyclic diolefins such as norbornadiene,5-ethylidenenorbornene, 5-vinylnorbornene and dicyclopentadiene,unsaturated esters such as ethyl acrylate and methyl methacrylate,lactones such as β-propiolactone, β-butyrolactone and γ-butyrolactone,lactams such as ε-caprolactam and δ-valerolactam, and epoxides such asepoxypropane and 1,2-epoxybutane.

Incidentally, the catalyst for polymerization of the present inventioncan be used not only for the polymerization of the above-mentionedolefin but also for the polymerization of a monomer other than theolefin.

In the present invention, no particular restriction is put on apolymerization method, and any of a slurry polymerization method, agaseous phase polymerization method, a bulk polymerization method, asolution polymerization method and a suspension polymerization methodcan be used, but the slurry polymerization method and the gaseous phasepolymerization method are preferable from the viewpoints of a highproductivity and less process steps.

With regard to the conditions of the polymerization, a polymerizationtemperature is usually in the range of -100° to 250° C., preferably -50°to 200° C., more preferably 0° to 130° C. Furthermore, a use ratio ofthe catalyst to the reaction material is such that the materialmonomer/the above-mentioned component (A) (molar ratio) is preferably inthe range of 1 to 10⁸, more preferably 100 to 10⁵. Moreover, apolymerization time is usually in the range of 5 minutes to 10 hours,and a reaction pressure is preferably in the range of from atmosphericpressure to 200 kg/cm² G, more preferably from atmospheric pressure to100 kg/cm² G.

The molecular weight of the polymer can be adjusted by selecting thekinds and the amounts of catalytic components and the polymerizationtemperature, and by carrying out the polymerization in the presence orabsence of hydrogen.

In the case that a polymerization solvent is employed, examples of theusable solvent include aromatic hydrocarbons such as benzene, toluene,xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane,cyclohexane and methylcyclohexane, aliphatic hydrocarbons such aspentane, hexane, heptane and octane, and halogenated hydrocarbons suchas chloroform and dichloromethane. These solvents may be used singly orin a combination of two or more thereof. In addition, a monomer such asan α-olefin may be used as the solvent. In a certain polymerizationmethod, the polymerization can be carried out in the absence of anysolvent.

No particular restriction is put on the molecular weight of the polymerwhich can be obtained by such a process, but its intrinsic viscosity η!(measured in decalin at 135° C.) is preferably 0.1 dl/g or more, morepreferably 0.2 dl/g or more. If the intrinsic viscosity is less than 0.1dl/g, sufficient mechanical properties cannot be obtained, and hence thepolymer having such a low intrinsic viscosity is not practical.

In the present invention, prepolymerization can be carried out by theuse of the above-mentioned catalyst for polymerization. Theprepolymerization can be accomplished by bringing a small amount of anolefin into contact with the solid catalytic component, but itsprocedure is not particularly limited and a known method can be used. Noparticular restriction is put on the olefin for use in theprepolymerization, and such olefins as mentioned above, for example,ethylene, α-olefins having 3 to 20 carbon atoms and mixtures thereof areusable, but it is advantageous to employ the same olefin as used in thepolymerization.

A prepolymerization temperature is usually in the range of -20° to 200°C., preferably -10° to 130° C., more preferably 0° to 80° C. In theprepolymerization, an inactive hydrocarbon, an aliphatic hydrocarbon, anaromatic hydrocarbon or a monomer can be used as the solvent. Above all,the aliphatic hydrocarbon is particularly preferable. Theprepolymerization may be carried out in the absence of any solvent.

In the prepolymerization, conditions are desirably regulated so that theintrinsic viscosity η! (measured in decalin at 135° C.) of aprepolymerized product may be 0.2 dl/g or more, preferably 0.5 dl/g ormore and so that the amount of the prepolymerized product per mmol ofthe transition metal component in the catalyst may be in the range of 1to 10,000 g, preferably 10 to 1,000 g.

Thus, an olefin polymer of the present invention having a uniformcomposition and a narrow molecular weight distribution can efficientlybe obtained.

Next, the present invention will be described in more detail withreference to examples, but the scope of the present invention should notbe limited at all by these examples.

REFERENCE PROPARATION EXAMPLE 1

Preparation of(1,1'-dimethylsilylene)(2,2'-dimethylsilylene)-bis(cyclo-pentadienyl)zirconiumdichloride (A-2)

2.4 g (9.6 mmol) of(1,1'-dimethylsilylene)(2,2'-dimethylsilylene)-bis(cyclopentadiene) wasdissolved in 50 ml of hexane, and 19.2 mmol of n-butyllithium (a hexanesolution containing n-butyllithium of 1.5 mol per liter of hexane) wasadded dropwise at -78° C. to the solution, followed by stirring at roomtemperature for 5 hours. Next, the solvent was distilled off, and theresultant residue was washed once with 20 ml of hexane, and then driedto obtain a white solid. Afterward, this solid was suspended in 50 ml oftoluene, and 2.3 g (9.6 mmol) of zirconium tetrachloride was added at-20° C. to the suspension. After stirring for 12 hours at roomtemperature, the solvent was distilled off, and recrystallization wasthen carried out from dichloromethane-hexane to obtain 1.1 g of(1,1'-dimethylsilylene)(2,2'-dimethylsilylene)-bis(cyclopenta-dienyl)zirconiumdichloride in the state of a colorless crystal.

The ¹ H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR (90 MHz, CDCl₃): δ 0.57 6H, s, (CH₃)₂ Si!, 0.93 6H, s, (CH₃)₂Si!, 6.47 (2H, t, --CH--), 6.98 (4H, d, --CH--).

Incidentally,(1,1'-dimethylsilylene)(2,2'-dimethylsilylene)-bis(cyclopentadiene) wassynthesized in accordance with a procedure described in"Organometallics", Vol. 10, p. 1787 (1991).

EXAMPLE 1

Preparation of(1,1'-dimethylsilylene)-(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconiumdichloride (A-1)

0.7 g (3.2 mmol) of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadiene) wasdissolved in 30 ml of hexane, and 6.48 mmol of n-butyllithium (a hexanesolution containing n-butyllithium of 1.5 mol per liter of hexane) wasadded dropwise at -78° C. to the solution, followed by stirring at roomtemperature for 5 hours. Next, the solvent was distilled off, and theresultant residue was washed with 20 ml of hexane, and the washed whitesolid was then dried under reduced pressure. Afterward, to the toluenesuspension (20 ml) of this solid, 0.8 g (3.2 mmol) of zirconiumtetrachloride was added, and after stirring for 12 hours at roomtemperature, the solvent was distilled off. Next, recrystallization wascarried out from dichloromethane-hexane to obtain 0.3 g of(1,1'-dimethylsilylene)-(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconiumdichloride in the state of a light yellow powder.

The ¹ H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR (90 MHz, CDCl₃): δ 1.01 3H, s, (CH₃)₂ Si!, 0.54 3H, s, (CH₃)₂Si!, 1.52 3H, s, (CH₃)₂ C!, 2.16 3H, s, (CH₃)₂ C!, 6.17 (2H, m, --CH--),6.53 (2H, m, --CH--), 6.82 (2H, m, --CH--).

Incidentally,(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadiene) wassynthesized in accordance with a procedure described in"Organometallics", Vol. 10, p. 3739 (1991).

EXAMPLE 2

In a 1-liter autoclave heated and dried under reduced pressure wereplaced 360 ml of toluene, 40 ml of 1-octene and 1 mmol oftriisobutylaluminum (TIBA) at room temperature under a nitrogenatmosphere, and the temperature of the solution was then raised up to60° C. with stirring. Afterward, 1 μmol of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconiumdichloride obtained in Example 1 and 1 μmol of N,N'-dimethylaniliniumtetrakis(pentafluorophenyl)borate were placed in the autoclave at 60°C., and the mixture was then heated up to 80° C. Next, while ethylenewas continuously introduced into the autoclave at 80° C. so as tomaintain 8 atm, polymerization was carried out for 1 hour.

After the completion of the reaction, the resultant reaction product waspoured into a methanol-hydrochloric acid solution, and then sufficientlystirred, followed by filtration. Next, the collected product wassufficiently washed with methanol, and then dried to obtain a polymer.The yield and characteristics of the obtained polymer were measured, andthe obtained results are shown in Table 1.

EXAMPLE 3

The same procedure as in Example 2 was repeated except that 1 mmol ofTIBA was replaced with 6 mmol of methylaluminoxane andN,N'-dimethylanilinium tetrakis-(pentafluorophenyl)borate was not used.The results are shown in Table 1.

EXAMPLE 4

The same procedure as in Example 2 was repeated except that 40 ml of1-octene was not used and a reaction time was set to 30 minutes. Theresults are shown in Table 1.

EXAMPLE 5

The same procedure as in Example 3 was repeated except that 40 ml of1-octene was not used and a reaction time was set to 30 minutes. Theresults are shown in Table 1.

Reference Example 1

The same procedure as in Example 2 was repeated except that(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconiumdichloride was replaced with(1,1'-dimethylsilylene)(2,2'-dimethylsilylene)-bis(cyclo-pentadienyl)zirconiumdichloride obtained in Reference Preparation Example 1. The results areshown in Table 1.

Reference Example 2

The same procedure as in Example 3 was repeated except that(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconiumdichloride was replaced with(1,1'-dimethylsilylene)(2,2'-dimethylsilylene)-bis(cyclo-pentadienyl)zirconiumdichloride obtained in Reference Preparation Example 1. The results areshown in Table 1.

Reference Example 3

The same procedure as in Example 4 was repeated except that(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconiumdichloride was replaced with(1,1'-dimethylsilylene)(2,2'-dimethylsilylene)-bis(cyclo-pentadienyl)zirconiumdichloride obtained in Reference Preparation Example 1. The results areshown in Table 1.

Reference Example 4

The same procedure as in Example 5 was repeated except that(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconiumdichloride was replaced with(1,1'-dimethylsilylene)(2,2'-dimethylsilylene)-bis(cyclo-pentadienyl)zirconiumdichloride obtained in Reference Preparation Example 1. The results areshown in Table 1.

                  TABLE 1-1                                                       ______________________________________                                               Catalyst         Polymer                                                      Main                         Yield                                            Catalyst                                                                            Cocatalyst Kind        (g)                                       ______________________________________                                        Example 2                                                                              A-1     TIBA       Ethylene-1-octene                                                                       45.7                                                     B-1        Copolymer                                         Example 3                                                                              A-1     MAO        Ethylene-1-octene                                                                       35.1                                                                Copolymer                                         Example 4                                                                              A-1     TIBA       Polyethylene                                                                            37.4                                                     B-1                                                          Example 5                                                                              A-1     MAO        Polyethylene                                                                            30.9                                    Ref. Ex. 1                                                                             A-2     TIBA       Ethylene-1-octene                                                                       29.5                                                     B-1        Copolymer                                         Ref. Ex. 2                                                                             A-2     MAO        Ethylene-1-octene                                                                       27.3                                                                Copolymer                                         Ref. Ex. 3                                                                             A-2     TIBA       Polyethylene                                                                            35.0                                                     B-1                                                          Ref. Ex. 4                                                                             A-2     MAO        Polyethylene                                                                            25.6                                    ______________________________________                                    

                  TABLE 1-2                                                       ______________________________________                                        Polymer                                                                       Intrinsic*                                                                    Viscosity                1-octene  Melting                                     η!      Melting point**                                                                           Unit Content                                                                            Energy**                                   (dl/g)       (°C.)                                                                              (mol %)   ΔH (J/q)                             ______________________________________                                        Example 2                                                                            0.92      108.7       5.8     22                                       Example 3                                                                            0.49      109.8       7.3     13                                       Example 4                                                                            2.37      133.5       --      200                                      Example 5                                                                            1.87      135.8       --      257                                      Ref. Ex. 1                                                                           0.80      115.6       4.0     92                                       Ref. Ex. 2                                                                           0.87      115.5       3.9     58                                       Ref. Ex. 3                                                                           2.82      135.0       --      200                                      Ref. Ex. 4                                                                           3.51      133.5       --      200                                      ______________________________________                                         *The intrinsic viscosity was measured in decalin at 135° C.            **The melting point was determined on the basis of the results of second      heat at a heating rate of 10° C./min by the use of DSC.           

As understood from Table 1, in the case that(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopenta-dienyl)zirconiumdichloride is used as a main catalytic component, the copolymerizabilityof ethylene-1-octene copolymerization is better than in the case that(1,1'-dimethylsilylene)(2,2'-dimethylsilylene)-bis(cyclopenta-dienyl)zirconiumdichloride is used.

EXAMPLE 6

Preparation of(1,1'-dimethylsilylene)-(2,2'-isopropylidene)-bis(cyclopentadienyl)titaniumdichloride (A-3)

2.3 g (10 mmol) of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadiene) wasdissolved in 100 ml of hexane, and 20 mmol of n-butyllithium was addeddropwise at -78° C. to the solution, followed by stirring at roomtemperature for 12 hours. Next, the solvent was distilled off, and theresultant residue was washed with 50 ml of hexane, and then dried underreduced pressure to obtain a white solid. Afterward, this solid wassuspended in 50 ml of tetrahydrofuran, and a tetrahydrofuran solutioncontaining 3.7 g (10 mmol) of a titanium trichloride-threetetrahydrofuran complex was added at -78° C. to the suspension. Next,the temperature of the solution was gradually returned to roomtemperature, followed by stirring for 12 hours. Afterward, 4.3 g (30mmol) of silver chloride was added to this suspension, and the mixturewas then stirred at room temperature for 2 days. The solvent wasdistilled off, and recrystallization was then carried out from ether toobtain 0.2 g of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)titaniumdichloride in the state of a red powder.

The ¹ H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR (90 MHz, CDCl₃): δ 0.43 3H, s, (CH₃)₂ Si!, 1.02 3H, s, (CH3)₂Si!, 1.36 (3H, S, (CH₃)₂ C), 2.18 (3H, S, (CH₃)₂ C), 6.3-7.1 (6H, m,--CH--).

In addition, some peaks attributed to impurities were slightly observed.

EXAMPLE 7

In a 1-liter autoclave heated and dried under reduced pressure wereplaced 360 ml of toluene, 40 ml of 1-octene and 1 mmol oftriisobutylaluminum (TIBA) at room temperature under a nitrogenatmosphere, and the temperature of the solution was then raised up to60° C. with stirring. Afterward, 1 μmol of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)titaniumdichloride obtained in Example 6 and 1 μmol of N,N'-dimethylaniliniumtetrakis(pentafluorophenyl)borate were placed in the autoclave at 60°C., and the mixture was then heated up to 80° C. Next, while ethylenewas continuously introduced into the autoclave at 80° C. so as tomaintain 8 atm, polymerization was carried out for 1 hour.

After the completion of the reaction, the resultant reaction product waspoured into a methanol-hydrochloric acid solution, and then sufficientlystirred, followed by filtration. Next, the collected product wassufficiently washed with methanol, and then dried to obtain a polymer.The results are shown in Table 2.

EXAMPLE 8

The same procedure as in Example 7 was repeated except that 1 mmol ofTIBA was replaced with 6 mmol of methylaluminoxane andN,N'-dimethylanilinium tetrakis(pentafluorophenyl)borate was not used.The results are shown in Table 2.

EXAMPLE 9

The same procedure as in Example 7 was repeated except that 40 ml of1-octene was not used. The results are shown in Table 2.

EXAMPLE 10

The same procedure as in Example 8 was repeated except that 40 ml of1-octene was not used. The results are shown in Table 2.

                  TABLE 2-1                                                       ______________________________________                                               Catalyst     Polymer                                                          Main                          Yield                                           Catalyst                                                                             Cocatalyst                                                                              Kind         (g)                                      ______________________________________                                        Example 7                                                                              A-3      TIBA      Ethylene-1-octene                                                                        0.85                                                     B-1       Copolymer                                         Example 8                                                                              A-3      MAO       Ethylene-1-octene                                                                        1.90                                                               Copolymer                                         Example 9                                                                              A-3      TIBA      Polyethylene                                                                             12.7                                                     B-1                                                         Example 10                                                                             A-3      MAO       Polyethylene                                                                             8.90                                   ______________________________________                                         A-3:                                                                          (1,1dimethylsilylene)(2,2isopropylidene)-bis(cyclopentadienyl)titanium ch    oride                                                                          ##STR31##                                                                

                  TABLE 2-2                                                       ______________________________________                                        Polymer                                                                       Intrinsic*                                                                    Viscosity   Melting 1-octene  Catalytic                                                                             Melting                                  η!     Point** Unit Content                                                                            Activity                                                                              Energy**                                (dl/g)      (°C.)                                                                          (mol %)   (kg/g Tihr)                                                                           ΔH (J/g)                          ______________________________________                                        Example 7                                                                            2.00     None    10.4    18      10.0                                  Example 8                                                                            2.96     None     9.8    40      11.3                                  Example 9                                                                            7.38     135     --      265     144                                   Example                                                                              --       134     --      186     126                                   10                                                                            ______________________________________                                         *The intrinsic viscosity was measured in decalin at 135° C.            **The melting point was determined on the basis of the results of second      heat at a heating rate of 10° C./min by the use of DSC.           

EXAMPLE 11

Preparation of(1,1'-dimethylsilylene)-(2,2'-isopropylidene)-bis(cyclopentadienyl)titaniumdichloride (A-4)

5.57 g (24.2 mmol) of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadiene) wasdissolved in 100 ml of THF (tetrahydrofuran), and 48.8 nmnol ofn-butyllithium was added dropwise at -78° C. to the solution, followedby stirring at room temperature for 8 hours. Next, the solvent wasdistilled off, and the resultant residue was washed with 100 ml ofhexane and next 100 ml of THF, and then dried under reduced pressure toobtain 1.00 g (4.16 mmol) of a white solid of a lithium salt. Afterward,this solid was suspended in 50 ml of tetrahydrofuran, and atetrahydrofuran solution (60 ml) containing 1.54 g (4.16 mmol) of atitanium trichloride-three tetrahydrofuran complex was added at roomtemperature to the suspension, followed by stirring for 12 hours. Next,11.08 g (77 mmol) of silver chloride was added to this suspension, andthe mixture was then stirred at room temperature for 3 hours. Thesolvent was distilled off, and extraction with ether, the removal ofether by distillation and washing with hexane were done in turn toobtain 35 mg of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)-titaniumdichloride in the state of a red powder.

The ¹ H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR (90 MHz, CDCl₃): δ 0.43 3H, s, (CH₃)₂ Si!, 1.02 3H, s, (CH₃)₂Si!, 1.36 (3H, s, (CH₃)₂ C), 2.18 (3H, s, (CH₃)₂ C), 6.3-7.1 (6H, m,--CH--).

EXAMPLE 12

In a 1-liter autoclave heated and dried under reduced pressure wereplaced 360 ml of toluene, 40 ml of 1-octene and 1 mmol oftriisobutylaluminum (TIBA) at room temperature under a nitrogenatmosphere, and the temperature of the solution was then raised up to60° C. with stirring. Afterward, 1 μmol of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)titaniumdichloride obtained in Example 11 and 1 μmol of N,N'-dimethylaniliniumtetrakis(pentafluorophenyl)borate were placed in the autoclave at 60°C., and the mixture was then heated up to 80° C. Next, while ethylenewas continuously introduced into the autoclave at 80° C. so as tomaintain 8 atm, polymerization was carried out for 1 hour.

After the completion of the reaction, the resultant reaction product waspoured into a methanol-hydrochloric acid solution, and then sufficientlystirred, followed by filtration. Next, the collected product wassufficiently washed with methanol, and then dried to obtain a polymer.

The results are shown in Table 3.

EXAMPLE 13

The same procedure as in Example 12 was repeated except that 1 mmol ofTIBA was replaced with 6 mmol of methylaluminoxane andN,N'-dimethylanilinium tetrakis(pentafluorophenyl)borate was not used.The results are shown in Table 3.

EXAMPLE 14

The same procedure as in Example 13 was repeated except that 3 μmol of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)titaniumdichloride and 3 mmol of methylaluminoxane were used and 560 ml oftoluene was used. The results are shown in Table 3.

EXAMPLE 15

The same procedure as in Example 14 was repeated except that 20 ml of1-octene and 580 ml of toluene were used. The results are shown in Table3.

                  TABLE 3-1                                                       ______________________________________                                                  Main Catalyst                                                                            Cocatalyst                                                                  Amount         Amount                                                  Kind   (μmol) Kind (μmol)                                   ______________________________________                                        Example 12  A-4    1         TIBA 1                                                                        B-1  1 × 10.sup.-3                         Example 13  A-4    1         MAO  6                                           Example 14  A-4    3         MAO  3                                           Example 15  A-4    3         MAO  3                                           ______________________________________                                    

                  TABLE 3-2                                                       ______________________________________                                                Ethylene                                                                             1-octene    Temp.   Time                                               (atm)  (ml)        (°C.)                                                                          (min)                                      ______________________________________                                        Example 12                                                                              8        40          80    60                                       Example 13                                                                              8        40          80    60                                       Example 14                                                                              8        40          80    60                                       Example 15                                                                              8        20          80    60                                       ______________________________________                                         A-4:                                                                          (1,1'-dimethylsilylene)(2,2'-isopropylidene)bis(cyclopentadienyl)titanium     dichloride (which is the same as the abovementioned A3)                       ##STR32##                                                                

                  TABLE 3-3                                                       ______________________________________                                                 Polymer                                                                                Intrinsic  1-octene                                                                             Melting                                                     Viscosity  Unit   Point.sup.*1                                         Yield   η!    Content                                                                              (Tm)                                                 (g)    (dl/g)     (mol %)                                                                              (°C.)                              ______________________________________                                        Example 12 4.3    0.90       9.2    67.3                                      Example 13 9.6    2.28       9.1    59.7                                      Example 14 39.6   3.85       5.1    85.2                                      Example 15 39.3   5.90       3.1    100.6                                     ______________________________________                                    

                  TABLE 3-4                                                       ______________________________________                                                 Polymer                                                                         Melting                                                                       Energy                                                                        ΔH (J/g)                                                                         MW.sup.*2 Mn.sup.*3                                                                           Q.sup.*4                                  ______________________________________                                        Example 12 45.2     39600     18000 2.2                                       Example 13 52.5     144000    66600 2.2                                       Example 14 43.9     223000    107000                                                                              2.1                                       Example 15 83.1     208000    101000                                                                              2.1                                       ______________________________________                                         *1: Melting point (Tm): The melting point was determined on the basis of      the results of second heat at a heating rate of 10° C./min by the      use of DSC, and in the case that it was 80° C. or less, it             represented a temperature at a broad peak.                                    *2: Mw: Weightaverage molecular weight                                        *3: Mn: Numberaverage molecular weight                                        *4: Q = Mw/Mn                                                            

EXAMPLE 16

Preparation of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(indenyl)zirconiumdichloride (A-5)

(1) In a 1-liter three-necked flask purged with nitrogen were placed10.8 g of magnesium and 45 ml of THF, and 0.6 ml of dibromomethane wasthen added dropwise thereto. After stirring for 5 minutes, the solventwas distilled off under reduced pressure, and 200 ml of THF was furtheradded. Next, a solution obtained by dissolving 18.3 g (0.105 mol) ofα,α'-dichloro-o-xylene in 300 ml of THF was added dropwise to the flaskat room temperature over 3 hours. After the completion of the dropping,the solution was further stirred for 15 hours and then cooled to -78°C., and a THF (100 ml) solution containing 6.8 g (36.2 mmol) of diethyldimethylmalonate was added dropwise over 1 hour. Afterward, thetemperature of the solution was returned to room temperature, and afterstirring for 2 hours, 100 ml of water was added at room temperature. Themixture was filtered with suction, and the solvent was then distilledoff under reduced pressure. Next, extraction was made withdichloromethane and a 1N aqueous ammonium chloride solution, and theresultant organic layer was washed twice with water and then dried overmagnesium sulfate. A solid was removed by filtration, and the solventwas then distilled off, thereby obtaining a yellow oil. Furthermore, theoil was purified through column chromatography using active alumina andthen recrystallized from hexane to obtain 4.8 g (15.9 mmol, yield: 44%)of a desired compound (hereinafter referred to as "Compound a") in thestate of a colorless crystal.

The ¹ H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR (CDCl₃): δ 1.235 (s, 6H, CH₃), 3.002 (d, J=16.4 Hz) and 3.470(d, J=16.4 Hz) (8H, CH₃), 3.767 (s, 2H, OH), 7.2-7.4 (mul, 8H, PhH)##STR33## wherein Me is a methyl group, and the same shall applyhereinafter.

(2) 4.8 g (15.9 mmol) of Compound a obtained in the paragraph (1) wasdissolved in 30 ml of dichloromethane, and 3.04 g (15.9 mmol) ofp-toluenesulfonic acid was added, followed by reflux for 8 hours. Theresultant reaction mixture was washed with sodium hydrogencarbonate andwater, and then dried over magnesium sulfate. A precipitate was removedby filtration, and the solvent was then distilled off, thereby obtaininga yellow oil. Furthermore, this oil was purified through columnchromatography using silica gel and then recrystallized from hexane toobtain 2.3 g (8.6 mmol, yield: 54%) of a desired compound (hereinafterreferred to as "Compound b") in the state of a colorless crystal.

The ¹ H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR (CDCl₃): δ 1.586 (s, 6H, CH₃), 3.470 (s, 4H, CH₂), 3.767 (s, 2H,CpH), 6.9-7.5 (mul, 8H, PhH) ##STR34##

(3) In a Schlenk tube purged with nitrogen were placed 6.2 g (22.7 mmol)of the Compound b obtained by repeating the reactions of theabove-mentioned (1) and (2) and 50 ml of diethyl ether. Next, thesolution was cooled to -78° C., and 28.4 ml (45.4 mmol) of ann-butyllithium solution having a concentration of 1.6 mol/liter wasadded dropwise thereto. The temperature of the solution was returned toroom temperature, and at this time, a white precipitate was graduallydeposited. After stirring at room temperature for 3 hours, thesupernatant liquid was drawn out, and the precipitate was washed twicewith a small amount of diethyl ether. Next, the precipitate was driedunder reduced pressure to obtain a dilithium salt (hereinafter referredto as "Compound c") in the state of a colorless powder: ##STR35##

(4) The dilithium salt (Compound c) obtained above was dissolved in 100ml of THF. Next, 3.0 g (22.7 mmol) of distilled dichlorodimethylsilanewas slowly added dropwise, followed by stirring for 3 hours. The solventwas distilled off, and extraction was then carried out withdichloromethane and water. The resultant organic layer was washed twicewith water, and then dehydrated over magnesium sulfate. Afterward, aprecipitate was removed by filtration, and recrystallization was thencarried out from hexane to obtain 6.5 g (19.6 mmol, yield: 86.5%) of acolorless crystal (the following Compound d).

The ¹ H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR (CDCl₃): δ -0.354 (s, 6H, SiCH₃), 1.608 (s, 6H, CCH₃), 3.347 (s,2H, SiCH), 6.785 (s, 2H, CpH), 6.9-7.6 (mul, 8H, PhH) ##STR36##

(5) In a Schlenk tube purged with nitrogen were placed 0.9 g (2.7 mmol)of the Compound b obtained in the above-mentioned (4) and 50 ml ofhexane. Next, the solution was cooled to 0° C., and 3.4 ml (5.4 mmol) ofan n-butyllithium solution having a concentration of 1.6 mol/liter wasadded dropwise thereto. The temperature of the solution was returned toroom temperature, and at this time, a white precipitate was deposited.After stirring at room temperature for 3 hours, the supernatant liquidwas drawn out, and the precipitate was washed twice with hexane. Next,the precipitate was dried under reduced pressure to obtain a dilithiumsalt (hereinafter referred to as "Compound e") in the state of a pinkpowder: ##STR37##

(6) Toluene was added to the dilithium salt (Compound e) obtained in theabove-mentioned (5) to form a suspension. Next, to this suspension, atoluene suspension containing 630 mg (2.7 mmol) of tetrachlorozirconiumwas added dropwise at 0° C. The temperature of the mixture was returnedto room temperature, and after stirring for 24 hours, a precipitate wasremoved by filtration and the solution was then concentrated. Afterward,recrystallization was done from toluene-hexane to obtain 240 mg (0.508mmol, yield: 19%) in the state of a yellowish orange crystal (A-5).

The ¹ H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR (heavy THF): δ -0.172 (s, 3H, SiCH₃), 0.749 (s, 3H, SiCH₃),1.346 (s, 3H, CCH₃), 2.141 (s, 3H, CCH₃), 3.654 (s, 2H, CpH), 6.692 (s,2H, CpH), 6.9-8.1 (mul, 8H, PhH) ##STR38##

EXAMPLE 17

In a 1-liter autoclave heated and dried under reduced pressure wereplaced 360 ml of toluene, 40 ml of 1-octene and 1 mmol oftriisobutylaluminum (TIBA) at room temperature under a nitrogenatmosphere, and the temperature of the solution was then raised up to60° C. with stirring. Afterward, 1 μmol of a zirconium-containingtransition metal complex (A-5) obtained in Example 16 and 1 μmol ofN,N'-dimethylanilinium tetrakis (pentafluorophenyl )borate were placedin the autoclave at 60° C., and the mixture was then heated up to 80° C.Next, while ethylene was continuously introduced into the autoclave at80° C. so as to maintain 8 atm, polymerization was carried out for 10minutes.

After the completion of the reaction, the resultant reaction product waspoured into a methanol-hydrochloric acid solution, and then sufficientlystirred, followed by filtration. Next, the collected product wassufficiently washed with methanol, and then dried to obtain a polymer.The results are shown in Table 4.

EXAMPLE 18

The same procedure as in Example 17 was repeated except that 1 mmol ofTIBA was replaced with 6 mmol of methylaluminoxane andN,N'-dimethylailinium tetrakis(pentafluorophenyl)borate was not used.The results are shown in Table 4.

EXAMPLES 19 and 20

Examples 19 and 20 were carried out in accordance with the sameprocedure as in Example 17 except that the amounts of components,reaction temperatures and times were set as shown in Table 4. Theresults are shown in Table 4.

                  TABLE 4-1                                                       ______________________________________                                                  Main Catalyst                                                                            Cocatalyst                                                                  Amount         Amount                                                  Kind   (μmol) Kind (μmol)                                   ______________________________________                                        Example 17  A-5    1         TIBA 1                                                                        B-1  1 × 10.sup.-3                         Example 18  A-5    1         MAO  6                                           Example 19  A-5    0.5       TIBA 1                                                                        B-1  5 × 10.sup.-4                         Example 20  A-5    0.5       TIBA 1                                                                        B-1  5 × 10.sup.-4                         ______________________________________                                         A-5: The zirconiumcontaining transition metal complex of Example 16      

                  TABLE 4-2                                                       ______________________________________                                                   Ethylene 1-octene   Temp. Time                                                (atm)    (ml)       (°C.)                                                                        (min)                                    ______________________________________                                        Example 17 8        40         80    10                                       Example 18 8        40         80    10                                       Example 19 9        40         50    60                                       Example 20 9        40         30    60                                       ______________________________________                                    

                  TABLE 4-3                                                       ______________________________________                                                 Polymer                                                                                Intrinsic  1-octene                                                                             Melting                                                     Viscosity  Unit   Point.sup.*1                                         Yield   η!    Content                                                                              (Tm)                                                 (g)    (dl/g)     (mol %)                                                                              (°C.)                              ______________________________________                                        Example 17 110.0  0.20       4.8    103                                       Example 18 38.4   0.31       4.6    104                                       Example 19 73.9   0.28       4.6    104                                       Example 20 16.5   0.37       6.1    94                                        ______________________________________                                    

                  TABLE 4-4                                                       ______________________________________                                                  Polymer                                                                         Melting                                                                       Energy                                                                        ΔH (J/g)                                                                         MW.sup.*2 Mn.sup.*3                                                                          Q.sup.*4                                  ______________________________________                                        Example 17  98.5     6900      2500 2.8                                       Example 18  108.9    10000     3200 3.14                                      Example 19  82.1     8100      3400 2.4                                       Example 20  56.4     4600      1100 4.3                                       ______________________________________                                         *1: Melting point (Tm): The melting point was determined on the basis of      the results of second heat at a heating rate of 10° C./min by the      use of DSC.                                                                   *2: Mw: Weightaverage molecular weight                                        *3: Mn: Numberaverage molecular weight                                        *4: Q = Mw/Mn                                                            

EXAMPLE 21

In a 1-liter autoclave heated and dried under reduced pressure wereplaced 400 ml of toluene and 6 mmol of methylaluminoxane at roomtemperature under a nitrogen atmosphere, and the temperature of thesolution was then raised up to 80° C. with stirring. Afterward, 20 mmolof(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclo-pentadienyl)zirconiumdichloride obtained in Example 1 was added thereto. Next, whilepropylene was continuously introduced into the autoclave so as tomaintain 3 atm, polymerization was carried out for 1 hour. After thecompletion of the reaction, the resultant reaction product was pouredinto a methanol-hydrochloric acid solution and then sufficientlystirred, and the solvent was distilled off. Next, the product was driedto obtain 26.2 g of an atactic polymer.

Reference Example 5

The same procedure as in Example 21 was repeated except that(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconiumdichloride was replaced with(1,1'-dimethylsilylene)(2,2'-dimethylsilylene)-bis(cyclo-pentadienyl)zirconiumdichloride obtained in Reference Preparation Example 1. As a result,11.3 g of an atactic polymer was obtained.

EXAMPLE 22

In a 1-liter autoclave heated and dried under reduced pressure wereplaced 480 ml of toluene under an argon atmosphere, and its temperaturewas then raised up to 150° C. Next, argon was introduced thereinto until11 kg/cm² G had been reached, and ethylene was then introduced so as toattain a total pressure of 24 kg/cm² G might. Afterward, 20 ml oftoluene, 6 mmol of methylaluminoxane and 5 μm of a zirconium complex(A-5) obtained in Example 16 which had previously been prepared in afeed pipe were fed to the autoclave, and ethylene was then continuouslyintroduced for 5 minutes so that a total pressure might be 35 kg/cm² G,whereby polymerization was carried out. The results are shown in Table5.

EXAMPLE 23

The same procedure as in Example 22 was repeated except that toluene wasreplaced with hexane. The results are shown in Table 5.

EXAMPLE 24

The same procedure as in Example 22 was repeated except that 480 ml oftoluene which was a solvent was replaced with 420 ml of hexane and 60 mlof 1-octene, and 1 μmol of a zirconium complex (A-5) was used. Theresults are shown in Table 5.

EXAMPLE 25

The same procedure as in Example 24 was repeated except that apolymerization temperature was changed to 170° C. The results are shownin Table 5.

                  TABLE 5-1                                                       ______________________________________                                                    Methyl-            Total                                          Catalyst    aluminoxane                                                                             1-octene Pressure                                                                              Temp.                                  (μmol)   (μmol) (ml)     (kg/cm.sup.3 G)                                                                       (°C.)                           ______________________________________                                        Example 22                                                                            5       6         0      35      150                                  Example 23                                                                            5       6         0      35      150                                  Example 24                                                                            1       6         60     35      150                                  Example 25                                                                            1       6         60     35      170                                  ______________________________________                                    

                  TABLE 5-2                                                       ______________________________________                                                     Polymer                                                                                Melting                                                         Time   Yield  Point*.sup.1                                                    (min)  (g)    (°C.)                                                                            Mw*.sup.2                                                                           Q*.sup.4                                ______________________________________                                        Example 22                                                                              5        97     124     5700  2.7                                   Example 23                                                                              5        91     124     5400  2.6                                   Example 24                                                                              5        28     121     5800  2.3                                   Example 25                                                                              5        3      117     5600  2.4                                   ______________________________________                                         *.sup.1 Melting point (Tm): The melting point was determined on the basis     of the results of second heat at a heating rate of 10° C./min by       the use of DSC.                                                               *.sup.2 Mw: Weightaverage molecular weight                                    *.sup.3 Q = Mw/Mn (weightaverage molecular weight)                       

Conditions for the measurement of the molecular weight and the molecularweight distribution were as follows.

Device: Waters ALC/GPC 150C

Column: Toso Co., Ltd., TSK HM+GMH6×2

Solvent: 1,2,4-trichlorobenzene

Temperature: 135° C.

Flow rate: This was measured in terms of polyethylene under conditionsof 1 ml/min by a GPC method.

EXAMPLE 26

(1) Preparation of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-4,4'-bis(trimethyltin)-bis(cyclopentadiene)(Compound f)

In a 300-ml Schlenk tube purged with nitrogen was placed 8.55 g (37.4mmol) of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadiene)(Compound g), and 150 ml of degassed and dried diethyl ether was furtheradded thereto. Next, the solution was cooled to -78° C. on a dryice-methanol bath. To this cooled solution, 45.9 ml (74.8 mmol) of ahexane solution containing 1.63 mol of n-butyl-lithium per liter ofhexane was added dropwise under a nitrogen gas stream with stirring, andthe solution was further stirred at room temperature for 12 hours,followed by filtration. The resultant residue was washed with 100 ml ofdegassed and dried hexane, and they dried under reduced pressure toobtain a dilithium salt.

Next, 8.90 g (37.0 mmol) of this dilithium salt was suspended in 150 mlof degassed and dried tetrahydrofuran, and the suspension was thencooled to -78° C. on a dry ice-methanol bath. While the cooledsuspension was stirred, a solution obtained by dissolving 14.8 g (74.8mmol) of trimethyltin chloride in 100 ml of degassed and driedtetrahydrofuran was added dropwise thereto. After further stirring atroom temperature for 4 hours, the solvent was distilled off underreduced pressure. Next, 150 ml of degassed and dried hexane was added tothe solution to carry out extraction, and the solvent was distilled offunder reduced pressure to obtain 15.07 g (27.2 mmol, yield: 73%) of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-4,4'-bis(trimethyltin)-bis(cyclopentadiene)(Compound f): ##STR39## (2) Preparation of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)titaniumdichloride (A-6)

In a 300-ml three-necked flask equipped with a reflux condenser andpurged with nitrogen was placed 6.15 g (11.1 mmol) of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-4,4'-bis(trimethyltin)-bis(cyclopentadiene)obtained in the above-mentioned (1), and 100 ml of degassed and driedtoluene was then added thereto. While this solution was stirred, 1.22 ml(11.1 mmol) of titanium tetrachloride diluted with 50 ml of degassed anddried toluene was added dropwise thereto under a nitrogen gas stream,and the solution was then heated under reflux for 4 hours on an oilbath. Next, the solvent was distilled off under reduced pressure, andthe resultant residue was washed with 100 ml of degassed and driedhexane and then 100 ml of degassed and dried diethyl ether. Afterward,the solution was dried under reduced pressure, and then extracted with200 ml of degassed and dried toluene. The extract was concentrated underreduced pressure, and then cooled to -20° C. to obtain 1.81 g (5.24mmol, yield: 47.2%)(1,1'-dimethylsilylene)-(2,2'-isopropylidene)-bis(cyclopentadienyl)titaniumdichloride in the state of a dark red crystal.

(3) Preparation of catalyst

Mixed were 2.0 g of silica (trade name Debison 952, made by Fuji DebisonCo., Ltd.) which had been calcined at 400° C. for 48 hours, 100 ml oftoluene and 30 mmol of methylaluminoxane, and the mixture was thenreacted at 40° C. for 2 hours. The resultant solid was collected byfiltration, and then sufficiently washed with toluene. Next, 100 ml oftoluene and 0.1 mmol of a titanium complex (A-6) obtained in theabove-mentioned (2) were added to the washed solid, and reaction wascarried out at 40° C. for 2 hours. The obtained solid was collected byfiltration, sufficiently washed with toluene, and then dried underreduced pressure to prepare a carried catalyst.

In this catalyst, there were contained 5.82 wt % of an aluminum atom and0.07 wt % of a titanium atom.

(4) Polymerization

In a 1-liter autoclave heated and dried under reduced pressure wereplaced 390 ml of hexane and 10 ml of 1-octene at room temperature in anitrogen atmosphere, and a carried catalyst (Al=7.0×10⁻⁴ mol,Ti=5.0×10⁻⁴ mol) obtained in the above-mentioned (3) was fed thereto,followed by heating the mixture up to 80° C. Afterward, while ethylenewas continuously fed thereto at 80° C. so as to maintain 8 atm,polymerization was carried out for 30 minutes to obtain 2.4 g of apolymer.

EXAMPLE 27

Preparation of(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3-methylindenyl)(3'-methylindenyl)-zirconiumdichloride (A-7)

(1) In a Schlenk tube purged with nitrogen were placed 6.0 g (18.3 mmol)of the Compound d obtained in Example 16 and 150 ml of diethyl ether.Next, the solution was cooled to 0° C., and 43.5 ml (73.2 mmol) of ann-butyl-lithium solution having a concentration of 1.6 mol/liter wasadded dropwise thereto. The temperature of the solution was returned toroom temperature, and at this time, a pink precipitate was graduallydeposited. After stirring at room temperature for 12 hours, the solventwas distilled off, and the precipitate was then washed twice withhexane. Next, the precipitate was dried under reduced pressure to obtaina dilithium salt (hereinafter referred to as "Compound e") in the stateof a pink powder.

(2) A dilithium salt (Compound e) obtained above was dissolved in 150 mlof THF, and 10.4 g (73.2 mmol) of methyl iodide was slowly addeddropwise at room temperature. Next, the solution was heated up to 50°C., and then stirred for 5 hours. Afterward, the solvent was distilledoff, and extraction was done with dichloromethane and water. Theresultant organic layer was washed twice with water, dehydrated overmagnesium sulfate, and then filtered. The solvent was distilled off,thereby obtaining 6.2 g (17.4 mmol) of a desired product (the followingCompound h) in the state of an oil: ##STR40##

(3) In a Schlenk tube purged with nitrogen were placed 6.2 g (17.4 mmol)of a Compound h and 150 ml of diethyl ether. Next, the solution wascooled to 0° C., and 43.5 ml (69.0 mmol) of an n-butyllithium solutionhaving a concentration of 1.6 mol/liter was added dropwise thereto. Thetemperature of the solution was returned to room temperature, and atthis time, a white precipitate was gradually deposited. After stirringat room temperature for 12 hours, the solvent was distilled off, and theprecipitate was washed twice with hexane. Next, the precipitate wasdried under reduced pressure to obtain a dilithium salt (the followingCompound i): ##STR41##

(4) 100 ml of toluene was added to the dilithium salt (Compound i)obtained above to form a suspension. In another Schlenk tube,tetrachlorozirconium (800 mg, 3.4 mmol) was mixed with 100 ml of tolueneto form another suspension, and this suspension was cooled to -78° C.Afterward, the above-mentioned suspension containing the dilithium saltwas slowly added dropwise to the cooled suspension. The temperature ofthe mixed suspension was returned to room temperature, and it was thenheated up to 80° C., followed by stirring for 6 hours. A precipitate wasremoved by filtration, and the solvent was then distilled off. After theresultant residue was washed with hexane, recrystallization was carriedout from diethyl ether to obtain 1.0 g of a yellow crystal which was thefollowing (A-7).

The ¹ H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR (CDCl₃): δ 0.89 (s, 3H, SiCH₃), 1.15 (s, 3H, SiCH₃), 1.92 (s,3H, CCH₃), 2.36 (s, 3H, CCH₃), 2.47 (s, 6H, CpCH₃), 6.9-7.6 (mul, 8H,Ind-H) ##STR42##

(5) Polymerization (i)

Preparation of ethylene-1-octene copolymer

In a 1-liter autoclave heated and dried under reduced pressure wereplaced 360 ml of toluene, 40 ml of 1-octene and 5 ml ofmethylaluminoxane (MAO) at room temperature in a nitrogen atmosphere,and the temperature of the solution was then raised up to 60° C. withstirring. Afterward, 1 μmol of the above-mentioned (A-7) was addedthereto, and the solution was then heated up to 80° C. Next, whileethylene was continuously introduced thereinto at 80° C. so as tomaintain 8 atm, polymerization was carried out for 20 minutes. After thecompletion of the reaction, the reaction solution was poured into amethanol-hydrochloric acid solution, and the resultant polymer waswashed three times with methanol, followed by drying under reducedpressure. The yield of the polymer was 54.4 g, and its melting point(Tm) was 108° C. and its intrinsic viscosity η! was 1.59 dl/g.

(6) Polymerization (ii)

The same procedure as in the above-mentioned (5) was repeated exceptthat 5 mmol of methylaluminoxane was replaced with 6 mmol oftetraisobutyldialuminoxane. Yield was 3.1 g.

(7) Polymerization (iii)

The same procedure as in the above-mentioned (6) was repeated exceptthat 6 mmol of tetraisobutyldialuminoxane was replaced with 1 μmol oftrisiobutylaluminum and 2 μmol of tris(pentafluorophenyl)borane. Yieldwas 2.5 g.

EXAMPLE 28

(1) Synthesis of ethyl(2-indenyl) acetate (Compound j)

Under a nitrogen gas stream, 3.3 g (0.14 mol) of sodium hydride wassuspended in 300 ml of THF, and the suspension was then cooled to 10° C.To the cooled suspension, a THF solution (200 ml of THF) containing 28.3g (0.11 mol) of ethyldiethyl phosphonoacetate was added dropwise over 1hour. After the dropping, the suspension was stirred at room temperaturefor 30 minutes, and then ice-cooled. Next, a THF solution (75 ml of THF)containing 16.3 g (0.12 mol) of 2-indanone was added dropwise over 1hour. After the dropping, the solution was stirred at room temperaturefor 30 minutes, and hydrolysis was carried out with water. Extractionwas done with 500 ml of diethyl ether, and the resultant organic layerwas then separated. This organic layer was dried over anhydrousmagnesium sulfate, and the solvent was then distilled off under reducedpressure. The resultant residue was subjected to vacuum distillation (3mmHg, 107°-117° C.), thereby obtaining a desired product (Compound k) inthe state of a light yellow oil.

The ¹ H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR (CDCl₃): 1.23 (t, 3H), 3.40 (s, 2H), 3.45 (s, 2H), 4.16 (q, 2H),6.65 (s, 1H)

(2) Synthesis of 2-(2-indenyl)-ethanol (Compound l)

Under a nitrogen gas stream, 2.2 g (58.49 mmol) of lithiumaluminumhydride was suspended in 100 ml of diethyl ether. To this suspension, adiethyl ether solution (50 ml of diethyl ether) containing 11 g (59.06mmol) of the above-mentioned compound k was added dropwise over 1 hour.After the dropping, the solution was stirred at room temperature for 30minutes. After ice-cooling, 50 ml of water was slowly added, and dilutehydrochloric acid was further added thereto so as to dissolveimpurities. The resultant oil layer was separated, and the solvent wasdistilled off under reduced pressure to obtain a desired compound(Compound 1) in the state of a white solid. Its yield was 7.89 g.

The ¹ H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR (CDCl₃): 1.56 (S, 1H), 2.76 (t, 2H), 3.37 (s, 2H), 3.83 (t, 2H)

(3) Synthesis of 1-bromo-2-indenylethane (Compound m)

Under a nitrogen gas stream, 4.61 g (28.77 mmol) of the above-mentionedCompound l was dissolved in 65 ml of dichloromethane. To this solution,7.66 g (29.20 mmol) of trimethylphosphine was added. Next, 5.19 g (29.16mmol) of N-bromosuccinimide was slowly added. After the addition ofN-bromosuccinimide, the solution was stirred at room temperature for 30minutes. Water was added to the reaction mixture, and the mixture wasfurther stirred. The resultant organic layer was separated and thendried over magnesium sulfate, and the solvent was distilled off underreduced pressure. The residue was purified through a silica gel column(developing solvent: hexane) to obtain a desired product (Compound m) inthe state of a colorless oil. Its yield was 5.07 g, i.e., 80.85%.

The ¹ H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR (CDCl₃): 3.20 (t, 2H), 3.32 (s, 2H), 3.52 (t, 2H), 6.60 (s, 1H),6.93-7.53 (m, 4H)

(4) Synthesis of (2,2'-ethylene)-(cyclopentadiene)-(indene) (Compound n)

Under a nitrogen gas stream, 18 mmol of a sodium salt of cyclopentadienewas dissolved in 100 ml of THF, and the solution was then cooled to -30°C. To this solution, a THF solution (30 ml of THF) containing 2 g (8.96mmol) of the above-mentioned Compound m was added dropwise over 1 hour.Next, the reaction mixture was stirred at room temperature for 16 hours,and then hydrolyzed. Extraction was carried out with dichloromethane,and the resultant oil layer was separated and then dried over anhydroussodium sulfate. Afterward, the solvent was distilled off under reducedpressure, and the residue was purified through a silica gel column(developing solvent: hexane) to obtain a desired product (Compound n) inthe state of a white solid. Its yield was 1.66 g, i.e., 59.4%.

The ¹ H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR: 2.73 (S, 4H), 2.91 (m, 2H), 3.30 (S, 2H), 5.95-6.65 (m, 4H),6.86-7.53 (m, 4H)

(5) Synthesis of(1,1'-dimethylsilylene)(2,2'-ethylene)-(cyclopentadiene)(indene)(Compound o)

1.66 g (7.96 mmol) of the above-mentioned Compound n was dissolved in100 ml of hexane, and the solution was then cooled to -78° C. To thissolution, 9.8 ml (15.97 mmol) of a hexane solution containing 1.63 mmolof n-butyllithium per ml of hexane was added dropwise over 30 minutes.After the completion of the dropping, the solution was stirred at roomtemperature for 12 hours. The resultant white precipitate was collectedby filtration and then washed with hexane, and the solvent was distilledoff under reduced pressure. In consequence, 1.51 g (6.85 mmol) of awhite powder (a dilithium salt of Compound n) was obtained. The thusobtained dilithium salt was dissolved in 100 ml of THF, and the solutionwas then cooled to -78° C. To this solution, a THF solution (50 ml ofTHF) containing 0.83 ml (6.83 mmol) of dichlorodimethylsilane was addeddropwise over 1 hour. After the completion of the dropping, the solutionwas stirred at room temperature for 6 hours, and THF was distilled offunder reduced pressure and extraction was then carried out withdichloromethane. Afterward, dichloromethane was distilled off underreduced pressure to obtain a Compound o. Its yield was 1.80 g. The ¹H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR (CDCl₃): 0.22 (s, 3H), 0.55 (s, 3H), 2.78 (s, 4H), 3.82-3.92(2H), 6.04-6.80 (m, 4H), 6.88-7.70 (m, 4H)

(6) Preparation of(1,1'-dimethylsilylene)(2,2'-ethylene)-(cyclopentadienyl)(indenyl)zirconiumdichloride (A-8)

100 ml of hexane was added to 1.80 g of the above-mentioned Compound o,and the solution was cooled to -78° C. To the cooled solution, 8.4 ml(13.7 mmol) of a hexane solution containing 1.63 mol of n-butyllithiumper liter of hexane was added dropwise over 1 hour. After the completionof the dropping, the temperature of the solution was raised to roomtemperature, followed by stirring for 12 hours. The resultant whiteprecipitate was collected by filtration, and then washed with hexane toobtain 1.80 g (6.51 mmol) of a dilithium salt of the Compound o. To thisdilithium salt, 100 ml of toluene was added, and the suspension was thencooled to -78° C. Next, a toluene suspension (50 ml of toluene)containing 1.5 g (6.44 mmol) of zirconium tetrachloride was added to thecooled suspension over about 30 minutes. Afterward, the temperature ofthe reaction mixture was raised to room temperature, and the mixture wasstirred for 12 hours as it was. Next, the supernatant liquid wascollected by filtration, and then evaporated to dryness under reducedpressure. The resultant residue was recrystallized from dichloromethaneand hexane, and extraction with heptane was then carried out. As aresult of this serial operation, a desired compound (A-8) was obtainedin the state of a light yellow solid. Its yield was 73 mg, i.e., 2.5%.

The ¹ H-NMR of this product was measured, and the following results wereobtained.

¹ H-NMR (CDCl₃): 0.11 (s, 3H), 0.19 (s, 3H), 3.15 (4H), 6.0-7.7 (m, 8H)##STR43##

(7) Polymerization of ethylene

In a heated and dried 1-liter autoclave were placed 400 ml of tolueneand 2.39 mmol of methylaluminoxane at room temperature under a nitrogengas stream. After the temperature of this mixture was raised up to 60°C., 2.27 μmol of the above-mentioned (A-8) was added thereto, and thismixture was further heated up to 80° C. When 80° C. had been reached,the pressure of ethylene was raised up to 8 kg/cm². In this state,polymerization was carried out for 30 minutes. After the completion ofthe reaction, the reaction product was poured into methanol, and theresultant polymer was collected by filtration, washed with methanol, andthen heated/dried under reduced pressure, thereby obtaining 78.6 g of apolyethylene. Its intrinsic viscosity η! was 3.07 dl/g.

Possibility of Industrial Utilization

A transition metal compound of the present invention is a novel multiplecrosslinking type compound, and it is useful as a catalytic componentfor olefin polymerization. Furthermore, according to a method of thepresent invention, this transition metal compound and a compound usableas a precursor of its ligand can efficiently be prepared. In addition, acatalyst for the olefin polymerization of the present invention has ahigh activity and an excellent copolymerizability, and so when thiscatalyst is used, an olefin polymer having a uniform composition and anarrow molecular weight distribution can efficiently be obtained.

We claim:
 1. A catalyst for olefin polymerization which comprises atransition metal compound represented by the general formula (I) belowand an activation cocatalyst, wherein the general formula (I) is##STR44## wherein M is Ti, Zr or Hf, E¹ and E² are each acyclopentadienyl group, a substituted cyclopentadienyl group, an indenylgroup or substituted indenyl group, and they form a crosslinkingstructure via (A¹)_(p), (A²)_(p), . . . (A^(n))_(p) and (D)_(s), andthey may be the same or different; X is a σ-bonding ligand, and when aplurality of Xs are present, these plural Xs may be the same ordifferent and each X may cross-link with E¹, E² or L; L is a Lewis base,and when a plurality of Ls are present, these plural Ls may be the sameor different, and each L may cross-link with E¹, E² or X; A¹, A², . . .A^(n) are each a crosslinking group consisting of at least one elementwhich is C, H, Si, O, N, S, or P and they may be the same or different,but at least one of them comprises a crosslink consisting of carbonalone; D is a crosslinking group consisting of at least one elementwhich is C, H, Si, O, N or P, and when a plurality of Ds are present,these plural Ds may be the same or different; n is an integer of 2 to 4;p is an integer of 1 to 4, and the respective ps may be the same ordifferent; q is an integer of 1 to 5 and is (the valence of M)-2; r isan integer of 0 to 3; and s is an integer of 0 to 4, and when s is 0,(A¹)_(p), (A²)_(p), . . . (A^(n))_(p) and E² form a direct bond.
 2. Thecatalyst for olefin polymerization according to claim 12 wherein atleast one of A¹, A², . . . A^(n) is a crosslinking group consisting of##STR45## wherein R is a hydrogen atom, a halogen atom, a hydrocarbongroup having 1 to 20 carbon atoms or halogen-containing hydrocarbongroup having 1 to 20 carbon atoms.
 3. The catalyst for olet-inpolymerization according to claim 1, wherein E¹ and E² are each acyclopentadienyl group or a substituted cyclopentadienyl group.
 4. Thecatalyst for olefin polymerization according to claim 2 wherein E¹ andE² are each a cyclopentadienyl group or a substituted cyclopentadienylgroup.
 5. The catalyst for olefin polymerization according to claim 2wherein at least one of E¹ and E² is an indenyl group or a substitutedindenyl group.
 6. A catalyst for olefin polymerization which comprises atransition metal compound represented by the general formula (II) and anactivation cocatalyst, where the general formula (II) is ##STR46##wherein M is Ti, Zr or Hf, E¹ and E² are each a cyclopentadienyl group,a substituted cyclopentadienyl group, an indenyl group or a substitutedindenyl group, and they form a cross-linking structure via (A¹)_(p),(A²), . . . (A^(n))_(p), and they may be the same or different; X is aσ-bonding ligand, and when a plurality of Xs are present, these pluralXs may be the same or different and each X may cross-link with E¹, E² orL; L is a Lewis base, and when a plurality of Ls are present, theseplural Ls may be the same or different, and each L may cross-link withE¹, E² or X; A¹, A², . . . A^(n) are each a crosslinking groupconsisting of at least one element which is C, H, Si, O, N, S or P andthey may be the same or different, but at least one of them comprises acrosslink consisting of carbon alone; n is an integer of 2 to 4; p is aninteger of 1 to 4, and the respective ps may be the same or different; qis an integer of 1 to 5 and is (the valence of M)-2; r is an integer of0 to
 3. 7. The catalyst for olefin polymerization according to 6 whereinat least one of Al¹, A², . . . A^(n) is a crosslinking group consistingof ##STR47## wherein R is a hydrogen atom, a halogen atom, a hydrocarbongroup having 1 to 20 carbon atoms or a halogen-containing hydrocarbongroup having 1 to 20 carbon atoms.
 8. The catalyst for olefinpolymerization according to claim 6, wherein E¹ and E² are each acyclopentadienyl group or a substituted cyclopentadienyl group.
 9. Thecatalyst for olefin polymerization according to claim 7 wherein E¹ andE² are each a cyclopentadienyl group or a substituted cyclopentadienylgroup.
 10. The catalyst for olefin polymerization according to claim 7wherein at least one of E¹ and E² is an indenyl group or a substitutedindenyl group.
 11. A catalyst for olefin polymerization which comprises(A) a transition metal compound according to the general formula (I)below and (B) a compound capable of reacting with the component (A) toform an ionic complex, where the general formula (I) is ##STR48##wherein M is ri, Zr or Hf. E¹ and E² are each a cyclopentadienyl group,a substituted cyclopentadienyl group, an indenyl group or substitutedindenyl group, and they form a cross-linking structure via (A¹)_(p),(A²)_(p), . . . (A¹)_(p) and (D)_(s), and they may be the same ordifferent; X is a σ-bonding ligand, and when a plurality of Xs arepresent, these plural Xs may be the same or different and each X maycross-link with E¹, E² or L; L is a Lewis base, and when a plurality ofLs are present, these plural Ls may be the same or different, and each Lmay cross-link with E¹, E² or X; A¹, A², . . . A^(n) are each acrosslinking group consisting of at least one element which is C, H, Si,O, N, S or P and they may be the same or different, but at least one ofthem comprises a crosslink consisting of carbon alone; D is acrosslinking group consisting of at least one element which is C, H, Si,O, N or P, and when a plurality of Ds are present, these plural Ds maybe the same or different; n is an integer of 2 to 4; p is an integer of1 to 4, and the respective ps may be the same or different; q is aninteger of 1 to 5 and is (the valence of M)-2; r is an integer of 0 to3; and s is an integer of 0 to 4, and when s is 0, (A¹)_(p), (A²)_(p), .. . (A^(n))_(p) and E² form a direct bond.
 12. The catalyst for olefinpolymerization according to 11 wherein at least one of A¹, A², . . .A^(n) is a crosslinking group consisting of ##STR49## wherein R is ahydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbonatoms or a halogen-containing hydrocarbon group having 1 to 20 carbonatoms.
 13. The catalyst for olefin polymerization according to claim 11,wherein E¹ and E2 are each a cyclopentadienyl group or a substitutedcyclopentadienyl group.
 14. The catalyst for olefin polymerizationaccording to claim 12 wherein E¹ and E² are each a cyclopentadienylgroup or a substituted cyclopentadienyl group.
 15. The catalyst forolefin polymerization according to claim 12 wherein at least one of E¹and E² is an indenyl group or a substituted indenyl group.
 16. Acatalyst for olefin polymerization which comprises (A) a transitionmetal compound according to the general formula (II) below and (B) acompound capable of reacting with the transition metal compound of thecomponent (A) to form an ionic complex, where the general formula (II)is ##STR50## wherein M is Ti, Zr or Hf, E¹ and E² are each acyclopentadienyl group, a substituted cyclopentadienyl group, an indenylgroup or a substituted indenyl group, and they form a cross-linkingstructure via (A¹)_(p), (A²), . . . (A^(n))_(p), and they may be thesame or different; X is a σ-bonding ligand, and when a plurality of Xsare present, these plural Xs may be the same or different and each X maycross-link with E¹, E² or L; L is a Lewis base, and when a plurality ofLs are present, these plural Ls may be the same or different, and eachI, may cross-link with E¹, E² or X; A¹, A², . . . A^(n) are each acrosslinking group consisting of at least on element which is C, H, Si,O, N, S or P and they may be the same or different, but at least one ofthem comprises a crosslink consisting of carbon alone; n is an integerof 2 to 4; p is an integer of 1 to 4, and the respective ps may be thesame or different; q is an integer of 1 to 5 and is (the valence ofM)-2; and r is an integer of 0 to
 3. 17. The catalyst for olefinpolymerization according to 16 wherein at least one of A¹, A², . . .A^(n) is a crosslinking group consisting of ##STR51## wherein R is ahydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbonatoms or a halogen-containing hydrocarbon group having 1 to 20 carbonatoms.
 18. The catalyst for olefin polymerization according to claim 16,wherein E¹ and E² are each a cyclopentadienyl group or a substitutedcyclopentadienyl group.
 19. The catalyst for olefin polymerizationaccording to claim 17 wherein E¹ and E² are each a cyclopentadienylgroup or a substituted cyclopentadienyl group.
 20. The catalyst forolefin polymerization according to claim 17 wherein at least one of E¹and E² is an indenyl group or a substituted indenyl group.
 21. Acatalyst for olefin polymerization which comprises (A) a transitionmetal compound according to the general formula (I) below, (B) acompound capable of reacting with the component (A) to form an ioniccomplex, and (C) an organic aluminum compound, where the general formula(I) is ##STR52## wherein M is Ti, Zr or Hf, E¹ and E² are each acyclopentadienyl group, a substituted cyclopentadienyl group, an indenylgroup or substituted indenyl group, and they form a cross-linkingstructure via (A¹)_(p), (A²)_(p), . . . (A^(n))_(p) and (D)_(s), andthey may be the same or different; X is a σ-bonding ligand, and when aplurality of Xs are present, these plural Xs may be the same ordifferent and each X may cross-link with E¹, E² or L; L is a Lewis base,and when a plurality of Ls are present, these plural Ls may be the sameor different, and each L may cross-link with E¹, E² or X; A¹, A², . . .A^(n) are each a crosslinking group consisting of at least one elementwhich is C, H, Si, O, N, S or P and they may be the same or different,but at least one of them comprises a crosslink consisting of carbonalone; D is a crosslinking group consisting of at least one elementwhich is C, H, Si, O, N or P, and when a plurality of Ds are present,these plural Ds may be the same or different; n is an integer of 2 to 4;p is an integer of 1 to 4, and the respective ps may be the same ordifferent; q is an integer of 1 to 5 and is (the valence of M)-2; r isan integer of 0 to 3; and s is an integer of 0 to 4, and when s is 0,(A¹)_(p), (A²)_(p), . . . (A^(n))_(p) and E² form a direct bond.
 22. Thecatalyst for olefin polymerization according to 21 wherein at least oneof A¹, A², . . . A^(n) is a crosslinking group consisting of ##STR53##wherein R is a hydrogen atom, a halogen atom, a hydrocarbon group having1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1to 20 carbon atoms.
 23. The catalyst for olefin polymerization accordingto claim 21, wherein E¹ and E² are each a cyclopentadienyl group or asubstituted cyclopentadienyl group.
 24. The catalyst for olefinpolymerization according to claim 22 wherein E¹ and E² are each acyclopentadienyl group or a substituted cyclopentadienyl group.
 25. Thecatalyst for olefin polymerization according to claim 22 wherein atleast one of E¹ and E² is an indenyl group or a substituted indenylgroup.
 26. A catalyst for olefin polymerization which comprises (A) atransition metal compound according to the general formula (II) below,(B) a compound capable of reacting with the transition metal compound ofthe component (A) to form an ionic complex, and (C) an organic aluminumcompound, where the general formula (II) is ##STR54## wherein M is Ti,Zr or Hf, E¹ and E² are each a cyclopentadienyl group, a substitutedcyclopentadienyl group, an indenyl group or a substituted indenyl group,and they form a cross-linking structure via (A¹)_(p), (A²), . . .(A^(n))_(p), and they may be the same or different; X is a σ-bondingligand, and when a plurality of Xs are present, these plural Xs may bethe same or different and each X may cross-link with E¹, E² or L; L is aLewis base, and when a plurality of Ls are present, these plural Ls maybe the same or different, and each L may cross-link with E¹, E² or X;A¹, A², . . . A^(n) are each a crosslinking group consisting of at leastone element which is C, H, Si, O, N, S or P and they may be the same ordifferent, but at least one of them comprises a crosslink consisting ofcarbon alone; n is an integer of 2 to 4; p is an integer of 1 to 4, andthe respective ps may be the same or different; q is an integer of 1 to5 and is (the valence of M)-2; and r is an integer of 0 to
 3. 27. Thecatalyst for olefin polymerization according to 26 wherein at least oneof A¹, A², . . . A^(n) is a crosslinking group consisting of ##STR55##wherein R is a hydrogen atom, a halogen atom, a hydrocarbon group having1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1to 20 carbon atoms.
 28. The catalyst for olefin polymerization accordingto claim 26, wherein E¹ and E² are each a cyclopentadienyl group or asubstituted cyclopentadienyl group.
 29. The catalyst for olefinpolymerization according to claim 27 wherein E¹ and E² are each acyclopentadienyl group or a substituted cyclopentadienyl group.
 30. Thecatalyst for olefin polymerization according to claim 27 wherein atleast one of E¹ and E² is an indenyl group or a substituted indenylgroup.
 31. A process for preparing an olefin polymer which comprises thestep of homopolymerizing a olefin, or copolymerizing an olefin, anotherolefin and/or another monomer other than the olefin in the presence of acatalyst for olefin polymerization as claimed in claim
 1. 32. A processfor preparing an olefin polymer which comprises the step ofhomopolymerizing an olefin, or copolymerizing an olefin, another olefinand/or another monomer other than the olefin in the presence of acatalyst for olefin polymerization as claimed in claim
 2. 33. A processfor preparing an olefin polymer which comprises the step ofhomopolymerizing a olefin, or copolymerizing an olefin, another olefinand/or another monomer other than the olefin in the presence of acatalyst for olefin polymerization as claimed in claim
 6. 34. A processfor preparing an olefin polymer which comprises the step ofhomopolymerizing an olefin, or copolymerizing an olefin, another olefinand/or another monomer other than the olefin in the presence of acatalyst for olefin polymerization as claimed in claim
 7. 35. A processfor preparing an olefin polymer which comprises the step ofhomopolymerizing a olefin, or copolymerizing an olefin, another olefinand/or another monomer other than the olefin in the presence of acatalyst for olefin polymerization as claimed in claim
 11. 36. A processfor preparing an olefin polymer which comprises the step ofhomopolymerizing an olefin, or copolymerizing an olefin, another olefinand/or another monomer other than the olefin in the presence of acatalyst for olefin polymerization as claimed in claim
 12. 37. A processfor preparing an olefin polymer which comprises the step ofhomopolymerizing a olefin, or copolymerizing an olefin, another olefinand/or another monomer other than the olefin in the presence of acatalyst for olefin polymerization as claimed in claim
 16. 38. A processfor preparing an olefin polymer which comprises the step ofhomopolymerizing an olefin, or copolymerizing an olefin, another olefinand/or another monomer other than the olefin in the presence of acatalyst for olefin polymerization as claimed in claim
 17. 39. A processaccording to claim 38, wherein the olefin is ethylene or propylene or amixture of ethylene with I-octene and wherein the transition, metalcompound (A) is(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)zirconium dichloride or(1,1'-dimethylsilylene)(2,2'-isopropylidene)-bis(cyclopentadienyl)titaniumdichloride.
 40. A process according to claim 38 wherein the olefin isethylene or propylene or a mixture of ethylene with I-octene and whereinthe transition metal compound (A) is(1,1'-dimethylsilylene)(2,2'-isopropylidene)-(3-methylindenyl)(3'-methylindenyl)-zirconium dichloride or(1,1'-dimethylsilylene)(2,2'-ethylene)-(cylopentadienyl)(indenyl)zirconium dichloride.
 41. A process for preparing an olefin polymerwhich comprises the step of homopolymerizing a olefin, or copolymerizingan olefin, another olefin and/or another monomer other than the olefinin the presence of a catalyst for olefin polymerization as claimed inclaim
 21. 42. A process for preparing an olefin polymer which comprisesthe step of homopolymerizing an olefin or copolymerizing an olefin,another olefin and/or another monomer other than the olefin in thepresence of a catalyst for olefin polymerization as claimed in claim 22.43. A process for preparing an olefin polymer which comprises the stepof homopolymerizing a olefin, or copolymerizing an olefin, anotherolefin and/or another monomer other than the olefin in the presence of acatalyst for olefin polymerization as claimed in claim
 26. 44. A processfor preparing an olefin polymer which comprises the step ofhomopolymerizing an olefin, or copolymerizing an olefin, another olefinand/or another monomer other than the olefin in the presence of acatalyst for olefin polymerization as claimed in claim 27.